[ CAS No. 4869-59-4 ] {[proInfo.proName]}

Name: 4869-59-4|3-Mercaptobenzoic acid|97%
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SKU: A394833
Price: 9.0 USD
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Quality Control of [ 4869-59-4 ]

COA NMR CNMR HPLC LC-MS

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SDS Specification

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Product Details of [ 4869-59-4 ]

CAS No. :	4869-59-4	MDL No. :	MFCD00238636
Formula :	C₇H₆O₂S	Boiling Point :	-
Linear Structure Formula :	-	InChI Key :	RSFDFESMVAIVKO-UHFFFAOYSA-N
M.W :	154.19	Pubchem ID :	95737
Synonyms :

Calculated chemistry of [ 4869-59-4 ]

Physicochemical Properties

Num. heavy atoms :	10
Num. arom. heavy atoms :	6
Fraction Csp3 :	0.0
Num. rotatable bonds :	1
Num. H-bond acceptors :	2.0
Num. H-bond donors :	1.0
Molar Refractivity :	40.65
TPSA :	76.1 Å²

Pharmacokinetics

GI absorption :	High
BBB permeant :	No
P-gp substrate :	No
CYP1A2 inhibitor :	No
CYP2C19 inhibitor :	No
CYP2C9 inhibitor :	No
CYP2D6 inhibitor :	No
CYP3A4 inhibitor :	No
Log Kp (skin permeation) :	-5.59 cm/s

Lipophilicity

Log Po/w (iLOGP) :	1.31
Log Po/w (XLOGP3) :	2.33
Log Po/w (WLOGP) :	1.67
Log Po/w (MLOGP) :	1.87
Log Po/w (SILICOS-IT) :	1.5
Consensus Log Po/w :	1.74

Druglikeness

Lipinski :	0.0
Ghose :	None
Veber :	0.0
Egan :	0.0
Muegge :	1.0
Bioavailability Score :	0.56

Water Solubility

Log S (ESOL) :	-2.64
Solubility :	0.352 mg/ml ; 0.00228 mol/l
Class :	Soluble
Log S (Ali) :	-3.57
Solubility :	0.0418 mg/ml ; 0.000271 mol/l
Class :	Soluble
Log S (SILICOS-IT) :	-1.87
Solubility :	2.1 mg/ml ; 0.0136 mol/l
Class :	Soluble

Medicinal Chemistry

PAINS :	0.0 alert
Brenk :	1.0 alert
Leadlikeness :	1.0
Synthetic accessibility :	1.0

Safety of [ 4869-59-4 ]

Signal Word:	Danger	Class:	8
Precautionary Statements:	P261-P280-P305+P351+P338	UN#:	3261
Hazard Statements:	H315-H318-H335	Packing Group:	Ⅲ
GHS Pictogram:

Application In Synthesis of [ 4869-59-4 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

Upstream synthesis route of [ 4869-59-4 ]
Downstream synthetic route of [ 4869-59-4 ]

[ 4869-59-4 ] Synthesis Path-Upstream 1~3

1
[ 4869-59-4 ]
[ 825-99-0 ]

Reference： [1] Journal of the Chemical Society, 1921, vol. 119, p. 1796

2
[ 4869-59-4 ]
[ 77-78-1 ]
[ 825-99-0 ]

Reference： [1] Patent: US2453232, 1943, ,

3
[ 4869-59-4 ]
[ 5345-27-7 ]

Reference： [1] Patent: US2453232, 1943, ,
[2] Journal of the Chemical Society, 1921, vol. 119, p. 1796

[ 4869-59-4 ] Synthesis Path-Downstream 1~78

1
[ 110-86-1 ]
[ 1227-49-2 ]
[ 4869-59-4 ]
[ 1234-18-0 ]

Reference： [1]Journal of the Chemical Society,1921,vol. 119,p. 1796

2
[ 1227-49-2 ]
furan-2,3,5(4H)-trione pyridine (1:1) [ No CAS ]
[ 4869-59-4 ]
[ 1234-18-0 ]

Reference： [1]Journal of the Chemical Society,1921,vol. 119,p. 1796

3
[ 1227-49-2 ]
[ 4869-59-4 ]

Reference： [1]Acta Pharmacologica et Toxicologica,1948,vol. 4,p. 199,201
[2]Journal of the Chemical Society,1921,vol. 119,p. 1796
[3]Inorganic Chemistry,2012,vol. 51,p. 9883 - 9892

4
[ 4869-59-4 ]
[ 1227-49-2 ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 4466 - 4476
[2]Journal of the Chemical Society,1921,vol. 119,p. 1796
[3]Chemische Berichte,1874,vol. 7,p. 795
[4]Zeitschrift fur Chemie,1870,p. 295
[5]Phosphorus, Sulfur and Silicon and the Related Elements,1992,vol. 73,p. 5 - 14

5
[ 4025-64-3 ]
[ 4869-59-4 ]

Yield	Reaction Conditions	Operation in experiment
92%		3-Chlorosulfonylbenzoic acid (156.0 g, 0.707 mol), acetic acid (240 mL), and red phosphorus (78.5 g, 2.53 mol) were placed in a 2-L three-neck flask. The mixture was heated to 110 C. and stirred while a solution of iodine (2.82 g, 0.011 mol) in acetic acid (66 mL) was added dropwise over about 30 min, so as to maintain the color of iodine vapor. The stirred mixture was cooled to 100 C. and treated dropwise with 41 mL (2.3 mol) of water over a 10-min period, then heated at reflux temperature for 1.5 h and subsequently cooled to 90 C. Following the addition of saturated sodium chloride solution (250 mL) and water (500 mL), the mixture was kept at 0-5 C. for 1 h and filtered. The damp filter cake was slurried with 450 mL of acetone, and the excess red phosphorus was removed by filtration; then the acetone was evaporated from the filtrate while adding 500 mL of water. The resultant solid was filtered off and dried under vacuum to give 100.1 g (92%) of 3-mercaptobenzoic acid, mp 138-141 C. (lit. mp 138-141 C.); 1H NMR (400 MHz, in CDCl3 w/TMS, ppm) 3.59 (s, SH), 7.36 (t, J=7.8 Hz, H-5), 7.51 and 7.90 (2d, J=7.8 Hz, H4 and H-6), 8.03 (s, H-2); {1H}13C NMR (100 MHz, in CDCl3 w/TMS, ppm) 171.77 (CO), 134.49 (C-4), 132.24 (C-1), 130.86 (C-2), 130.34 C-3), 129.42 (C-5), 127.59 (C-6).
62%	With hydrogenchloride; zinc; In benzene; for 1h;Heating / reflux;	3-MERCAPTO-BENZOIC acid (44a). To a suspension of 3- (chlorosulfonyl) benzoic acid (22.0 g, 0.10 mol) and zinc powder (87.5 g, 1.3 mol) in benzene (150 mL) was added at 0 C, in a dropwise manner, concentrated hydrochloric acid (150 mL, 10 M). The mixture was heated at reflux, stirred for 1 hour, cooled to room temperature, and filtered through a pad of celite, which was subsequently washed with benzene (3 x 50 mL). The organic layer was separated and washed with water (100 mL), and brine (100 mL), dried over anhydrous MGS04, filtered and concentrated under reduced pressure to give a white solid which was recrystallised from aqueous ethanol (9.5 g, 62%) to give the title compound as a solid, mp 147 C.

Reference： [1]Patent: US2005/49307,2005,A1 .Location in patent: Page/Page column 5
[2]Journal of Heterocyclic Chemistry,1982,vol. 19,p. 961 - 965
[3]Synthesis,2009,p. 3211 - 3213
[4]Patent: WO2004/46094,2004,A1 .Location in patent: Page 62-63
[5]Patent: US2453232,1943,
[6]Helvetica Chimica Acta,1939,vol. 22,p. 601,609
[7]Journal of the Chemical Society,1921,vol. 119,p. 1796
[8]Organic Syntheses,1963,vol. Coll. Vol. IV,p. 695,697
[9]Phosphorus, Sulfur and Silicon and the Related Elements,1992,vol. 73,p. 5 - 14

6
[ 4869-59-4 ]
[ 108-24-7 ]
[ 90887-44-8 ]

Yield	Reaction Conditions	Operation in experiment
88%		Acetic anhydride (0.46 mL, 4.86 mmol) was added at 00C to a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (11, 250 mg, 1.62 mmol) in 1 M aqueous NaOH solution (5.0 mL, 5.0 mmol) . The mixture was stirred at 00C for 1 h. A precipitate was formed. The mixture was acidified by the addition of 1 M aqueous HCl solution and filtered. The solid was dried i.v. to afford 3- (acetylthio)benzoic acid (12; 280 mg, 88%) .
88%	With sodium hydroxide; In water; at 0℃; for 1h;	Acetic anhydride (0.46 mL, 4.86 mmol) was added at 0 C. to a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (11, 250 mg, 1.62 mmol) in 1 M aqueous NaOH solution (5.0 mL, 5.0 mmol). The mixture was stirred at 0 C. for 1 h. A precipitate was formed. The mixture was acidified by the addition of 1 M aqueous HCl solution and filtered. The solid was dried i.v. to afford 3-(acetylthio)benzoic acid (12; 280 mg, 88%).
88%	With sodium hydroxide; at 0℃; for 1h;	Acetic anhydride (0.46 mL, 4.86 mmol) was added at 0 C. to a soln of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (11, 250 mg, 1.62 mmol) in 1 M aq. NaOH soln (5.0 mL, 5.0 mmol). The mixture was stirred at 0 C. for 1 h. A precipitate formed; and the mixture was acidified by the addition of 1 M aq. HCl soln and filtered. The solid was dried i.v. to afford 3-(acetylthio)benzoic acid (12; 280 mg, 88%) (cf. Scheme 1).

88%	With sodium hydroxide; In water; at 0℃; for 1h;	At 0 C, acetic acid unitary dry (0 · 46mL, 4 · 86mmol) was added 3_ sparse acid (11,250mg, 1. 62mmol)The 1Mu NaOH solution (5.0mL, 5.0mmol) was added. The mixture was stirred at 0 C for 1 hour. A precipitate formed . Join1Mu HC1 aqueous mixture was acidified and filtered . The solid was dried in vacuo to provide 3- ( S -acetyl ) benzoic acid (12; 280mg, 88%).
88%	With sodium hydroxide; In water; at 0℃; for 1h;	Acetic anhydride (0.46 mL, 4.86 mmol) was added at 0C to asolution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (11, 250 mg, 1.62 mmol) in 1M aqueous NaOH solution (5.0 mL, 5.0 mmol). The mixture wasstirred at 0C for 1 h. A precipitate was formed. The mixture was acidified by the addition of 1 M aqueous HCl solution and filtered. The solid was dried l.v. to afford 3-(acetylthio)benzoic acid (12; 280 mg, 88%).
88%	With sodium hydroxide; In water; at 0℃; for 1h;	Acetic anhydride (0.46 mL, 4.86 mmol) was added at 0 C. to a soln of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (11 250 mg, 1.62 mmol) in 1 M aq. NaOH soln (5.0 mL, 5.0 mmol). The mixture was stirred at 0 C. for 1 h. A precipitate formed; and the mixture was acidified by the addition of 1 M aq. HQ soln and filtered. The solid was dried i.v. to afford 3-(acetylthio) benzoic acid (12; 280 mg, 88%) (cf. Scheme 1).

Reference： [1]Patent: WO2011/15241,2011,A1 .Location in patent: Page/Page column 203
[2]Patent: US2012/202821,2012,A1 .Location in patent: Page/Page column 123; 242
[3]Patent: US2012/270881,2012,A1 .Location in patent: Page/Page column 123
[4]Patent: CN105294732,2016,A .Location in patent: Paragraph 0910; 1406
[5]Patent: JP2015/155430,2015,A .Location in patent: Paragraph 0120; 0131
[6]Patent: JP2017/160247,2017,A .Location in patent: Paragraph 0103; 0131
[7]Journal of the American Chemical Society,1956,vol. 78,p. 854,859

7
[ 1227-49-2 ]
[ 62-53-3 ]
[ 4869-59-4 ]
[ 1234-18-0 ]

Reference： [1]Journal of the Chemical Society,1921,vol. 119,p. 1796

8
[ 4869-59-4 ]
[ 70-11-1 ]
3-phenacylmercapto-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In ethanol;Heating / reflux;	To bromoacetophenone (250 mg, 1. 16 mmole) and anhydrous K2CO3 (694 mg, 5.02 mmole) in ethanol, 193.6 mg (1.25 mmole) <strong>[4869-59-4]3-mercaptobenzoic acid</strong> was added and the mixture refluxed overnight. The solvent was evaporated and water added to the solid residue. The basic aqueous solution was extracted with ethyl acetate to remove unreacted bromoacetophenone. The aqueous layer was acidified and extracted with ethyl acetate, dried, evaporated and the residue purified by flash chromatography using chloroform: methanol 95: 5. Evaporation of the fractions resulted in a yellow powder (380 mg). M. S. M/S 271 (M-1) + 1H NMR (DMSO) 84. 75 (2H, s,-CH2-), 7.39-7. 7 (4H, M, 4 X ARH), 7.75 (1H, d, ARH, J= 5.61 Hz), 7.86 (1H, s, ArH), 8.02 (3H, d, ArH).

Reference： [1]Chemische Berichte,1939,vol. 72,p. 1257,1269
[2]Patent: WO2004/58747,2004,A1 .Location in patent: Page 44

9
[ 4869-59-4 ]
[ 80-40-0 ]
[ 5537-74-6 ]

Reference： [1]Journal of the Chemical Society,1928,p. 3004

10
[ 4869-59-4 ]
[ 77-78-1 ]
[ 825-99-0 ]

Reference： [1]Patent: US2453232,1943,

11
[ 50-00-0 ]
[ 619-26-1 ]
[ 4869-59-4 ]
3-[Methyl-(3-nitro-phenyl)-amino]-methylsulfanyl}-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	at 80℃; for 2h;

Reference： [1]Eldin, Sherif; Jencks, William P. [Journal of the American Chemical Society, 1995, vol. 117, # 17, p. 4851 - 4857]

12
[ 4869-59-4 ]
air [ No CAS ]
[ 1227-49-2 ]

Reference： [1]Chemische Berichte,1874,vol. 7,p. 795

13
[ 67-56-1 ]
[ 4869-59-4 ]
[ 72886-42-1 ]

Yield	Reaction Conditions	Operation in experiment
85.9%		To a solution of 3 g (0.01946 mol) of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> in 30 ml of methanol, cooled to 0-50C, 0.53 ml of concentrated sulphuric acid (95-98%) were carefully added. The reaction mixture was warmed to room temperature and then refluxed for 2.5 hours. After this time, the mixture was cooled to 0-50C and 0.13 ml more of concentrated sulphuric acid (95-98%) were carefully added. The reaction mixture was refluxed for 1.5 hours and then stirred at room temperature for 16 hours. The solvent was removed under reduced pressure and the residue was dissolved in ethyl acetate. The obtained solution was washed with 4% aqueous solution of NaHCO3 (x2), water and brine. The organic layer was separated, dried (MgSO4), and concentrated. The title compound was obtained as an oil. (2.81 g, 85.9%).
77%	With sulfuric acid; for 4h;Reflux;	[00205] A mixture of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (1.52 g, 9.86 mmol) and sulfuric acid (3 mL) was refluxed in methanol (30 mL) for 4h. The mixture was concentrated to a small volume under vacuum and diethyl ether, followed by water were added. The product was extracted with diethyl ether and the combined organic extracts were washed successively with sat. NaHC03 and brine, then dried over MgS04 and concentrated under vacuum to give 1.28 g of the title compound as a pale yellow oil (77%).
	With sulfuric acid; for 24h;Reflux;	[0113] 3-Mercaptobenzoic acid (10.0 g) was suspended in methanol (310 mL), added with sulfuric acid (0.3 mL), andstirred for 24 hours under reflux with heating. After cooling to room temperature, the solvent was evaporated underreduced pressure and water was added to residues. After adjusting to pH 8 by using a saturated aqueous solution ofsodium hydrogen carbonate, it was extracted with ethyl acetate and dried over anhydrous sodium sulfate. After distillingthe solvent under reduced pressure, the residues were purified by silica gel column chromatography (10% ethyl acetate/hexane) to obtain the title compound as a colorless oil.1H-NMR (CDCl3) delta: 7.95 (1H, dd, J = 2.0, 1.5 Hz), 7.82 (1H, ddd, J = 7.7, 1.5, 1.3 Hz), 7.45 (1H, ddd, J = 7.9, 2.0, 1.3Hz), 7.31 (1H, dd, J = 7.9, 7.7 Hz), 3.91 (3H, s), 3.54 (1H, s).

	With sulfuric acid; at 85℃; for 1h;	To a solution of <strong>[4869-59-4]3-sulfanylbenzoic acid</strong> (200 mg, 1.30 mmol) in methanol (10 mL) were added H2SO4 (1 ml). The reaction mixture was stirred at 85 C for 1 h. Water (20 mL) and EtOAc (30 mL) were added. The aqueous phase was extrated with Ethyl acetate (20 mL*2), the combined organic phases were washed with brine, dried over Na2S04, filtered and evaporated to dryness to obtain methyl 3-sulfanylbenzoate.
	With hydrogenchloride; for 1h;Heating / reflux;	3-Mercaptobenzoic acid methyl ester (45a). To a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (4.8 g, 31 mmol) in methanol (50 mL) at 0 C was added a solution of hydrochloric acid in methanol (1M, 200 mL, 0.2 mol). The mixture was heated at reflux, stirred for 1 hour and concentrated under reduced pressure. The residue was taken up in ethyl acetate and the solution was washed consecutively with saturated aqueous sodium hydrogen carbonate (100 mL), distilled water (100 mL), and brine (100 mL). The organic layer was dried over anhydrous MgS04, filtered and concentrated under reduced pressure to give the title compound as a colourless oil.

Reference： [1]Journal of Medicinal Chemistry,2000,vol. 43,p. 2664 - 2674
[2]Patent: WO2007/124898,2007,A1 .Location in patent: Page/Page column 52
[3]Patent: WO2012/42265,2012,A1 .Location in patent: Page/Page column 56
[4]Patent: EP2840076,2015,A1 .Location in patent: Paragraph 0113
[5]Angewandte Chemie - International Edition,2016,vol. 55,p. 7821 - 7825
Angew. Chem.,2016,vol. 128,p. 7952 - 7956,5
[6]Patent: WO2016/120403,2016,A1 .Location in patent: Page/Page column 219
[7]Patent: WO2004/46094,2004,A1 .Location in patent: Page 63

14
[ 24424-99-5 ]
[ 4869-59-4 ]
[ 323191-90-8 ]

Reference： [1]Journal of Medicinal Chemistry,2002,vol. 45,p. 177 - 188

15
[ 4869-59-4 ]
[ 83794-86-9 ]

Yield	Reaction Conditions	Operation in experiment
22%	With lithium aluminium tetrahydride; In tetrahydrofuran; at 0 - 20℃;Inert atmosphere;	To a stirred solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (1 g, 6.5 mmol) in THF (10 mL) was added LiAlH4 (246 mg, 13 mmol) at 0oC portion wise. After addition, the mixture was stirred at room temperature under N2 overnight. The reaction mixture was quenched by addition of NaSO4.10H2O at 0oC, filtered, the filtrate was concentrated to give crude product, which was purified by CC on silica gel eluting with PE : EA =4:1 to give (3-mercaptophenyl)methanol as a colorless oil (200 mg, yield 22.0 %).1H NMR (400 MHz, DMSO-d6) delta 7.25 (s, 1 H), 7.11 - 7.22 (m, 2 H), 7.02 - 7.08 (m, 1 H), 5.35 (s, 1 H), 5.19 (t, J = 5.69 Hz, 1 H), 4.43 (d, J = 5.63 Hz, 2 H).

Reference： [1]Journal of Medicinal Chemistry,2004,vol. 47,p. 18 - 21
[2]Patent: WO2019/140387,2019,A1 .Location in patent: Paragraph 00450-00452
[3]Journal of Heterocyclic Chemistry,1982,vol. 19,p. 961 - 965

16
[ 4869-59-4 ]
[ 74-88-4 ]
[ 90721-40-7 ]

Yield	Reaction Conditions	Operation in experiment
96%	With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 0 - 20℃; for 1h;	Methyl iodide (0.972 mL) was added to a mixture of 3-mercapto-benzoic acid (601 mg, 3.9 mmol) and potassium carbonate (2.7 g, 19.5 mmol) in DMF (8 mL) in an ice-bath. After the reaction was warmed to room temperature and stirred for 1 hour, the reaction mixture was diluted with ethyl acetate, washed with water (3X), dried over anhydrous sodium sulfate, filtered, and concentrated to afford 3-methylsulfanyl-benzoic acid methyl ester (684 mg, 96%, yellow [OIL). 1H] NMR [(CDC13),] [S] (ppm): 7.90 (s, 1H), 7.80 (d, [1H),] 7.44 (d, 1H), 7.35 (t, 1H), 3.92 (s, 3H), 2.53 (s, 3H). 3-Methylsulfanyl-benzoic acid methyl ester (684mg, 3.8 mmol) and 1N [NAOH] (5.6 mL, 5.6 mmol) in methanol (8 [ML)] and THF (8 mL) were heated at [70C] for 1 hour. The reaction mixture was concentrated and then the residue was diluted with water. After acidification with 1N [HC1] to [PH-2,] the aqueous layer was extracted with ethyl acetate and then washed with water and saturated brine, dried over anhydrous sodium sulfate, filtered, and concentrated to afford 3-methylsulfanyl-benzoic acid (616 mg, 97%, white [SOLID). 1H] NMR (DMSO), [8] (ppm): 13.1 (bs, [1H),] 7.76 (s, 1H), 7.70 (d, 1H), 7.51 (d, 1H), 7.44 (t, 1H), 2.52 (s, 3H).
96%	With potassium carbonate; In DMF (N,N-dimethyl-formamide); at 0 - 20℃; for 1h;	Methyl iodide (0.972 mL) was added to a mixture of 3-mercapto-benzoic acid (601 mg, 3.9 mmol) and potassium carbonate (2.7 g, 19.5 mmol) in DMF (8 [ML)] in an ice-bath. After the reaction was warmed to room temperature and stirred for 1 hour, the reaction mixture was diluted with ethyl acetate, washed with water (3X), dried over anhydrous sodium sulfate, filtered, and concentrated to afford [3-METHYLSULFANYL-BENZOIC] acid methyl ester (684 mg, 96%, yellow [OIL). 1H] NMR (CDC13), [8] (ppm): 7.90 (s, 1H), 7.80 (d, 1H), 7.44 (d, 1H), 7.35 (t, 1H), 3.92 (s, 3H), 2.53 (s, 3H).

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2005,vol. 15,p. 4136 - 4142
[2]Patent: WO2004/14881,2004,A2 .Location in patent: Page 136
[3]Patent: WO2004/14370,2004,A2 .Location in patent: Page/Page column 60

17
[ 67-56-1 ]
[ 3034-22-8 ]
[ 4869-59-4 ]
[ 439578-76-4 ]

Reference： [1]Bioorganic and Medicinal Chemistry Letters,2006,vol. 16,p. 3706 - 3712

18
[ 4869-59-4 ]
[ 25906-66-5 ]
C₃₀H₁₈O₁₂S₆ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide at 20℃;

Reference： [1]Vial, Laurent; Ludlow, R. Frederick; Leclaire, Julien; Perez-Fernandez, Ruth; Otto, Sijbren [Journal of the American Chemical Society, 2006, vol. 128, # 31, p. 10253 - 10257]

19
[ 4869-59-4 ]
[ 25906-66-5 ]
C₃₀H₁₈O₁₂S₆ [ No CAS ]
C₃₂H₁₆O₁₆S₈ [ No CAS ]
[ 1227-49-2 ]

Reference： [1]Journal of the American Chemical Society,2006,vol. 128,p. 10253 - 10257

20
[ 4869-59-4 ]
[ 5345-27-7 ]

Reference： [1]Patent: US2453232,1943,
[2]Journal of the Chemical Society,1921,vol. 119,p. 1796

21
[ 4869-59-4 ]
[ 825-99-0 ]

Reference： [1]Journal of the Chemical Society,1921,vol. 119,p. 1796

22
[ 4869-59-4 ]
[ 1822-51-1 ]
[ 668262-21-3 ]

Yield	Reaction Conditions	Operation in experiment
	With sodium hydroxide; In ethanol; water; at 75℃; for 1h;	Water (10 [ML)] was added to a flask containing <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (2. [08] g, 13.5 mmol, Aldrich) and sodium hydroxide (1.16 g, 29.0 [COOL).] To the resulting solution was added 4-picolyl chloride hydrochloride (2.31 g, 14.1 mmol, Aldrich) and ethanol (20 mL). The mixture was heated in a [75 C] oil bath for 1 hour and then added to a separatory funnel with 100 [ML] of water and 100 [ML] of [CHZCLZ.] This resulted in a suspension in the aqueous layer. This suspension was washed with an additional 100 [ML] of CH2C12 and then filtered. The solid was then dried at [100 C] under vacuum yielding 2.80 g of white solid.

Reference： [1]Patent: WO2004/18414,2004,A2 .Location in patent: Page 77

23
[ 4869-59-4 ]
[ 50916-55-7 ]
3-[2-(3-cyanophenyl)-2-oxoethylsulfanyl]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate In ethanol Heating / reflux;	Bromoacetylbenzonitrile (300 mg, 1.34 mmole) and anhydrous K2CO3 (740 mg, 5.35 mmole) in ethanol, 210 mg (1.36 mmole) 3-mercaptobenzoic acid was added and the mixture refluxed overnight. The solvent was evaporated and water added to the solid residue. The basic aqueous solution was extracted with ethyl acetate to remove unreacted - BROMOACETYLBENZONITRILE. The aqueous layer was acidified and extracted with ethyl acetate, dried, evaporated and the residue purified by flash chromatography using chloroform followed by chloroform: methanol (99: 1). Evaporation of high Rf yellow fractions resulted in a yellow powder (130 mg). M. S. m/s 296 (M-1) + 1H NMR (DMSO) 8 4.31 (2H, s, -CH2-), 7.25-8. 25 (8H, m, 8 x ArH)

Reference： [1]Current Patent Assignee: THE BURNET INSTITUTE - WO2004/58747, 2004, A1 Location in patent: Page 45

24
[ 104-76-7 ]
[ 4869-59-4 ]
[ 86705-33-1 ]

Yield	Reaction Conditions	Operation in experiment
95%	With sulfuric acid; In toluene; for 6h;Heating / reflux;	2-Ethyl-1-hexanol (44.4 g, 0.341 mol), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (35.0 g, 0.227 mol), toluene (250 mL) (or other suitable solvent forming an azeotrope with water), and concentrated sulfuric acid (0.2 mL) were placed in a 500-mL three-neck round-bottom flask equipped with a magnetic stirring bar, a water separator, and a reflux condenser. After the mixture had been heated under reflux with stirring for 6 h, the solid <strong>[4869-59-4]3-mercaptobenzoic acid</strong> had disappeared, and 4.14 mL (0.230 mol) of water had been collected by the water separator. The mixture was allowed to cool to room temperature and washed in succession with 20 mL of saturated NaHCO3 solution and two 50-mL portions of brine. Then the organic layer was dried over anhydrous MgSO4 and freed of solvent by rotary evaporation under vacuum to give 57.2 g (95%) of residual 2-ethylhexyl 3-mercaptobenzoate as a mobile straw-colored oil; 1H NMR (400 MHz, in CDCl3 w/TMS, ppm) 0.89-0.97 (m, 6H, 2CH3), 1.30-1.48 (m, 8H, 4CH2), 1.67-1.76 (m, 1H, CH), 3.56 (s, 1H, SH), 4.19-4.27 (m, 2H, OCH2), 7.30 (t, J=7.8 Hz, H-5), 7.43 and 7.81 (2d, J=8.0 Hz, H-4 and H-6), 7.94 (t, J=1.8 Hz, H-2); {1H}13C NMR (100 MHz, in CDCl3 w/TMS, ppm) 166.17 (CO), 133.50 (C4), 131.86 and 131.65 (C-1 and C-3), 130.29 (C-2), 129.24 (C-5), 126.91 (C-6), as well as 67.85, 39.21, 30.88, 29.33, 24.30, 23.32, 14.43, and 11.44 (8 aliphatic Cs).

Reference： [1]Patent: US2005/49307,2005,A1 .Location in patent: Page/Page column 6

25
[ 4869-59-4 ]
[ 111-46-6 ]
di(ethylene glycol) bis(3-mercaptobenzoate) [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
99%	With sulfuric acid; In toluene; for 6h;Heating / reflux;	Di(ethylene glycol) (19.0 g, 0.179 mol), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (57.9 g, 0.376 mol), toluene (250 mL), and concentrated sulfuric acid (0.2 mL) were placed in a 500-mL three-neck round-bottom flask equipped with a magnetic stirring bar, a water separator, and a reflux condenser. After the mixture had been heated under reflux with stirring for 6 h, the solid <strong>[4869-59-4]3-mercaptobenzoic acid</strong> had disappeared, and 6.50 mL (0.361 mol) of water had been collected by the water separator. The mixture was allowed to cool to room temperature and washed in succession with 20 mL of saturated NaHCO3 solution and two 50-mL portions of brine. Then the organic layer was dried over anhydrous MgSO4 and freed of solvent by rotary evaporation under vacuum to give 67.4 g (99%) of residual di(ethylene glycol) bis(3-mercaptobenzoate) as a viscous straw-colored oil; 1H NMR (400 MHz, in CDCl3 w/TMS, ppm) 3.56 (s, 2H, 2SH), 3.87 (t, J=4.6 Hz, 4H, CH2OCH2), 4.49 (t, J=4.6 Hz, 4H, 2CH2O2C), 7.26 (t, J=8.0 Hz, H-5), 7.42 and 7.79 (2d, J=7.6 Hz, H-4 and H-6), 7.92 (s, H-2); {1H}13C NMR (100 MHz, in CDCl3w/TMS, ppm) 165.98 (CO), 133.67 (C-4), 131.98 (C-1), 131.03 (C-3), 130.36 (C-2), 129.26 (C-5), 127.02 (C-6), 69.38 (CH2OCH2), 64.44 (2CH2O2C).

Reference： [1]Patent: US2005/49307,2005,A1 .Location in patent: Page/Page column 11

26
[ 4869-59-4 ]
[ 350-46-9 ]
[ 264224-08-0 ]

Yield	Reaction Conditions	Operation in experiment
		[0628] 3-[(4-Nitrophenyl)thiolbenzoic Acid [0629] A suspension of potassium carbonate (18 g) in acetone (140 mL) at ambient temperature was treated with <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (10 g, 64.4 mmol, 1 eq) followed by 4-nitrofluorobenzene (18 g, 127.7 mmol, 2 eq). The resultant mixture was stirred for 18 h and then poured onto saturated sodium bicarbonate and washed with ethyl acetate. The basic aqueous layer was acidified with 5N HCl and extracted into ethyl acetate (3×100 mL). The combined organics were dried with anhydrous sodium sulphate and concentrated in vacuo to give the product as a solid. [0630] 1H NMR (DMSO): delta7.35 (2H, d), 7.66 (1H, t), 7.81 (1H, m), 8.06 (2H, m), 8.16 (2H, d), and 13.31 (1H, bs). [0631] MS (APCI-ve): (M-H]- at m/z 274 (C13H9NO4S requires [M-H]- at m/z 274)

Reference： [1]Patent: US2004/10031,2004,A1 .Location in patent: Page/Page column 24

27
[ 4869-59-4 ]
[ 133692-18-9 ]
3-[(2-Aminothiazol-5-yl)thio]benzoic Acid Ethyl Ester [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
75%	With hydrogenchloride; sodium methylate; In 1,4-dioxane; methanol;	A. 3-[(2-Aminothiazol-5-yl)thio]benzoic Acid Ethyl Ester A 4.37 M solution of sodium methoxide in methanol (10 mL, 43.7 mmol) was added dropwise to a stirred suspension of 2-amino-5-bromothiazole hydrochloride (2.16 g, 10 mmol) and <strong>[4869-59-4]3-carboxythiophenol</strong> (1.85 g, 12 mmol) in methanol (75 mL) at 0-5 C. The solution was allowed to warm to rt. for 2 h and a 4 M solution of hydrogen chloride in dioxane (15 mL, 60 mmol) was added. The suspension was stirred at rt. overnight and concentrated. The crude residue was diluted with satd. aqueous sodium bicarbonate solution (50 mL). The precipitated solid was filtered and washed with water (20 mL, 5) and ether (20 mL, 5). The solid was filtered and dried in vacuo at 60 C. to obtain the titled compound (1.97 g, 75%).

Reference： [1]Patent: US2003/69238,2003,A1

28
[ 4869-59-4 ]
[ 174258-32-3 ]
3-[3-[(5-methyl-2-phenyl-4-oxazolyl)methoxy]benzylthio]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With triethylamine; In N,N-dimethyl-formamide; at 1 - 30℃; for 1h;	To a mixture of 4-(3-chloromethylphenoxymethyl)-5-methyl-2-phenyloxazole (3.00 g), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (1.47 g) and N,N-dimethylformamide (30 mL) was dropwise added triethylamine (2.13 g) at room temperature. The reaction mixture was stirred at room temperature for 1 hr. The reaction mixture was poured into water, acidified with 2N hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give crystals (3.70 g, yield 90%) of 3-[3-[(5-methyl-2-phenyl-4-oxazolyl)methoxy]benzylthio]benzoic acid from a fraction eluted with acetone-hexane (1:1, v/v). Recrystallization from ethyl acetate gave colorless prism crystals. melting point: 129-130 DEG C.

Reference： [1]Patent: EP1357115,2003,A1 .Location in patent: Page/Page column 74

29
[ 918538-08-6 ]
[ 4869-59-4 ]
3-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)pyrrolo[1,2-f][1,2,4]triazin-2-ylthio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
67%	In butan-1-ol; at 170℃; for 15h;	Example 4; 3-({4-[(3-cyclopropyl-1H-pyrazol-5-yl)amino]pyrrolo[2,1-f][1,2,4]triazin-2-yl}sulfanyl)-N-methylbenzamide; 4A. 3-(4-(5-cyclopropyl-1H-pyrazol-3-ylamino)pyrrolo[1,2-f][1,2,4]triazin-2-ylthio)benzoic acid; A mixture of 2A (99 mg, 0.36 mmol) and <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (278 mg, 5 equiv) in 1.0 mL n-BuOH was heated in a Smith Synthesizer microwave reactor (Personal Chemistry, Sweden) at 170 C. for 15 hr. After cooling to RT, the mixture was diluted with MeOH, and the precipitate was collected by filtration to give 95 mg 4A (67% yield). 1H NMR (DMSO-d6 with a drop of D2O): 0.49 (m, 2H), 0.86 (m, 2H), 1.70 (m, 1H), 5.61 (s, 1H), 6.61 (m, 1H), 7.25 (m, 1H), 7.60 (m, 2H), 7.85 (m, 1H),8.03 (m, 1H), 8.11 (s, 1H); MS: 393 (M+H)+; and RP HPLC ret. t.: 1.76 min (Phenomenex-Luna S10: 4.6×50 mm column, 3 min gradient, 4 mL/min).

Reference： [1]Patent: US2007/4731,2007,A1 .Location in patent: Page/Page column 16-17

30
[ 944924-78-1 ]
[ 4869-59-4 ]
3-(5-Phenyl-[1,2,4]triazolo[4,3-a]quinolin-8-ylsulfanyl)-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine;tris-(dibenzylideneacetone)dipalladium(0); 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 20 - 70℃; for 0.5h;Sealed tube;	Step 1: 3-(5-Phenyl-[1,2,4]triazolo[4,3-a]quinolin-8-ylsulfanyl)-benzoic acid (11a) 8-Iodo-5-phenyl-[1,2,4]triazolo[4,3-a]quinoline (250 mg, 0.67 mmol), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (120 mg, 0.81 mmol), iPr2NEt (0.36 mL, 2.1 mmol), Pd2dba3 (15 mg, 0.02 mmol), and 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (19 mg, 0.03 mmol) were dissolved in 1,4-dioxane and degassed with N2. The reaction was then sealed and heated to 70 C. for 30 minutes, followed by cooling to room temperature, filtration, and concentration to give the desired product, 11a.

Reference： [1]Patent: US2007/173508,2007,A1 .Location in patent: Page/Page column 119

31
[ 20511-12-0 ]
[ 4869-59-4 ]
[ 1027785-47-2 ]

Yield	Reaction Conditions	Operation in experiment
34%	With potassium phosphate; dimethylaminoacetic acid;copper(l) iodide; In N,N-dimethyl-formamide; at 120℃; for 2h;	A) A procedure described in Syn. Lett. 1254, 2004 was followed. To solution of 2-amino-5-iodopyridine (220 mg, 1 mmol) in dimethyl formamide (2 mL) were added sequentially <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (185 mg, 1.2 mmol), CuI (50 mg), N,N-dimethylglycine (50 mg) and K3PO4 (1.06 g). The mixture was heated to 120 0C for 2 h, cooled to RT and water was added. The solid was filtered and the filtrate was treated with IN HCl to adjust the solution to peta 4. The solid formed was collected by filtration, dissolved in IN nuaOeta and the solution was filtered. The filtrate was purified by RP etaPLC eluting with a mixture of methanol in water containing 0.1% TFA to obtain 3-(6-aminopyridin-3-ylthio)benzoic acid (84 mg, 34%). LC/MS; (M+eta)+ = 247.

Reference： [1]Patent: WO2008/60907,2008,A2 .Location in patent: Page/Page column 42

32
[ 7436-85-3 ]
[ 4869-59-4 ]
[ 1039630-90-4 ]

Yield	Reaction Conditions	Operation in experiment
55%	With sodium hydroxide; In tetrahydrofuran; water; at 0 - 20℃;	B. Preparation of ethyl 3-(3-amino-lH-pyrazol-5-ylthio)benzoate1) Preparation of 3,3-bis-(3-sulfanyl-benzoic acid)acrylonitrile <n="34"/>[00127] To a stirred solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (5.3g, 34.4 mmol) and sodium hydroxide (2.75g, 68.9 mmol) in water (100 mL) at 00C, was added a solution of 3,3-dichloroacrylonitrile (2.Og, 16.4 mmol) in tetrahydrofuran (10 mL). The reaction was allowed to reach room temperature and stirred overnight. The mixture was then acidified with cone, hydrochloric acid, extracted with ethyl acetate, dried over anhydrous magnesium sulphate, filtered and concentrated. The residue was crystallized in ethyl acetate to give the title material (3.2g, 55%) as a solid along with the impure material (3.0g). 1H NMR 400 MHz DMSO-d6 delta (ppm): 5.75 (IH, s), 7.52 - 7.63 (3H, m), 7.67 - 7.72 (IH, m), 7.74 - 7.80 (IH, m), 7.82 - 7.88 (IH, m), 7.96 - 8.02 (2H, m), 13.28 (2H, s).

Reference： [1]Patent: WO2008/86128,2008,A2 .Location in patent: Page/Page column 32-33

33
[ 4869-59-4 ]
[ 168296-33-1 ]
6-per-deoxy-6-per-(3-carboxyphenyl)thio-γ-cyclodextrin, sodium salt [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Triphenylphosphine (30.1 g, 15 eq) was dissolved with stirring in dry DMF (160 ml). To this was added iodine (30.5 g, 15.6 eq) over 10 min. with heat evolved. Dry gamma-cyclodextrin (10 g, 7.7 mmol) was then added and the mixture was heated to 70 C. for 24 h. The mixture was allowed to cool, to which sodium methoxide (3.1 g sodium in 50 ml methanol) was added and the mixture was stirred for 30 min, before pouring onto methanol (800 ml) and evaporating to dryness. To the residue was added water (500 ml) and the solid was collected by filtration and washed with water (3×100 ml), then acetone (3×100 ml), and dried under vacuum at 70 C. to give 6-per-deoxy-6-per-iodo-gamma-cyclodextrin as a yellow solid (16.2 g) which was used without further purification. [00077] To a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (1.0 g, 10 eq) in DMF (30 ml) was added 60% sodium hydride dispersed in oil (476 mg, 22 eq) portionwise over 30 min. The mixture was cooled and 6-per-deoxy-6-per-iodo-gamma-cyclodextrin (1.4 g) in DMF (30 ml) was added. The mixture was then stirred at 70 C. for 24 h. The mixture was allowed to cool to room temperature and quenched with the addition of water (20 ml) before evaporating to a low volume. The solution was poured into acetone (500 ml) and the precipitate was collected by filtration, dissolved in water (20 ml) and dialysed (MWCO 1000) by changing the external water four times. Internal solution was evaporated to low volume and poured into acetone (250 ml). The solid precipitate was collected by filtration and dried under vacuum at 70 C. to afford the title compound (1.45 g) as a white solid: 1H NMR (D2O) delta 7.77 (8H, br s, Ar-H), 7.55 (8H, d, J=6.0 Hz, Ar-H), 7.71 (16H, m, Ar-H), 5.16 (8H, s, CyD 1-H), 4.00-3.94 (16H, m, CyD 3,5-H), 3.58-3.53 (16H, m, CyD 4,2-H), 3.43-3.40 (8H, m, CyD 6-H), 3.24-3.20 (8H, m, CyD 6-H); Electrospray m/z 1190.6 for [M-8Na+6H]2-, calcd for C104H104Na8O48S8 M 2562.39.

Reference： [1]Patent: US6670340,2003,B1 .Location in patent: Page column 8-9

34
[ 639858-58-5 ]
[ 4869-59-4 ]
3-[2-(pyridin-2-ylamino)thiazol-5-ylmethylsulfanyl]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		A mixture of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (308 mg, 2 mmol) and sodium hydride (60% in oil, 160 mg, 4 mmol) was stirred at RT under argon for 10 min and then cooled to 0 C. and (5-chloromethyl-thiazol-2-yl)pyridin-2-yl-amine hydrochloride salt (262 mg, 1 mmol) was added. The resulting reaction mixture was stirred at 0 C. for 1 h and acidified with 1N potassium hydrogen sulfate solution to pH=4. The mixture was filtered and the collected solid was washed with water and dried in vacuo to provide compound 11A, 3-[2-(pyridin-2-ylamino)thiazol-5-ylmethylsulfanyl]benzoic acid, which was used directly for the next step.

Reference： [1]Patent: US2004/77696,2004,A1 .Location in patent: Page/Page column 12

35
[ 4869-59-4 ]
[ 121-44-8 ]
triethylammonium hemi(3,3'-disulfanediyldibenzoate) [ No CAS ]

Reference： [1]Synthesis,2008,p. 2023 - 2032

36
[ 4869-59-4 ]
[ 817-09-4 ]
[ 1078132-64-5 ]

Reference： [1]Chemical Communications,2008,p. 4180 - 4182

37
C₂₀H₂₂N₄O₈S₂ [ No CAS ]
[ 4869-59-4 ]
C₁₀H₁₂N₂O₄S [ No CAS ]
C₁₇H₁₆N₂O₆S₂ [ No CAS ]
[ 1227-49-2 ]

Reference： [1]Chemical Communications,2008,p. 5301 - 5303

38
[ 75-45-6 ]
[ 4869-59-4 ]
[ 4837-24-5 ]

Yield	Reaction Conditions	Operation in experiment
		To a dioxane (150 mL) solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (25.0 g, 0.162 mol) were added water (50 mL) and sodium hydroxide (40 g, 1.0 mol), followed by heating under stirring at 60C. Therein was bubbled Flon 22 (difluorochloromethane) gas for 9 hours. Fron 22 was bubbled in at such a rate that it was gently refluxed by means of a gas trap cooled with dry ice-acetone, and during the time, each 10 g of sodium hydroxide was further added twice. After completion of the reaction, dioxane was removed by evaporation and then the residue was acidified by adding concentrated hydrochloric acid. The resulting residue was dissolved in ethyl acetate and insoluble matter was filtrated through Celite (trade name). Thereafter, the filtrate was washed with water and brine and then the solvent was removed by evaporation. Based on NMR inspection of the residue, the ratio of 3-(difluoromethylthio)benzoic acid to the starting material was found to be about 9:1. Subsequently, thionyl chloride (28.4 g, 0.239 mol) and toluene (30 mL) were added to crude 3-(difluoromethylthio)benzoic acid (32.5 g) obtained above, followed by heating under stirring at 100C for 1 hour. After completion of the reaction, the solvent was removed by evaporation to obtain a crude acid chloride. Then, the acid chloride obtained above was added to a mixed solution of ethanol (100 mL) and triethylamine (24.1 g, 0.239 mol) cooled with ice-water, followed by stirring at room temperature for 3 hours. After completion of the reaction, the solvent was removed by evaporation and the obtained residue was dissolved in ethyl acetate. The solution was washed with water and brine and then the solvent was removed by evaporation. The residue was purified on a silica gel column (Kiesel gel 60 manufactured by MERCK, 2% AcOEt-Hex) to obtain ethyl 3-(difluoromethylthio)benzoate (30.7 g, 84%).1H-NMR (400MHz, CDCl3) : 1.41(t, 3H, J=7.2Hz), 4.40(q, 2H, J=7.2Hz), 6.86(t, 1H, J=56.8Hz), 7.48(t, 1H, J=8.0Hz), 7.77(dt, 1H, J=8.0Hz, 1.6Hz), 8.10(dt, 1H, J=8.0Hz, 1.6Hz), 8.25(t, 1H, J=1.6Hz).

Reference： [1]Patent: EP1544202,2005,A1 .Location in patent: Page/Page column 50-51

39
[ 618-51-9 ]
[ 4869-59-4 ]

Yield	Reaction Conditions	Operation in experiment
92%	With sodiumsulfide nonahydrate; copper; ethane-1,2-dithiol; In dimethyl sulfoxide; at 100℃; for 20h;Inert atmosphere; Green chemistry;	General procedure: To a test tube containing a magnetic bar was added aryl iodide(1 mmol), copper powder (6.35 mg, 0.1 mmol), Na2S·9H2O(720.54 mg, 3 mmol), and DMSO (2 mL). After flushing withargon, 1,2-ethanedithiol (8.4 muL, 0.1 mmol) was added. Themixture was stirred in the oil bath at 100 C for 20 h. Aftercooled to ambient temperature, the reaction mixture was distributedin aq HCl (5%) and EtOAc. The organic layer was separated and washed with water and brine, dried, and concentratedunder vacuum. The crude product was further purifiedby column chromatography using ethyl acetate/n-hexane aseluent to provide the desired aryl thiol.

Reference： [1]Advanced Synthesis and Catalysis,2015,vol. 357,p. 2205 - 2212
[2]Synlett,2017,vol. 28,p. 2272 - 2276
[3]Organic Letters,2009,vol. 11,p. 5250 - 5253

40
[ 1220052-06-1 ]
[ 4869-59-4 ]
[ 1220052-17-4 ]
[ 1227-49-2 ]
4,6-bis(hydroxymethyl)dibenzothiophene [ No CAS ]

Reference： [1]Journal of the American Chemical Society,2010,vol. 132,p. 4466 - 4476

41
[ 1241507-32-3 ]
[ 4869-59-4 ]
[ 1241507-33-4 ]

Yield	Reaction Conditions	Operation in experiment
100%	With caesium carbonate;dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; In N,N-dimethyl-formamide; at 90℃; for 24h;Inert atmosphere;	c. 3-{3-[3-(2-Morpholin-4-yl-ethoxy)-phenyl]-[1,2,4]triazolo[4,3-a]pyridin-6- ylsulfanylj-benzoic acid; A reaction vessel was charged with Example 1 step b (400 mg, 0.888 mmol), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (205 mg, 1.24 mmol), [1 ,1'- bis(diphenylphosphino)ferrocene] dichloropalladium(ll) 1 :1 complex with DCM (138 mg, 0.168 mmol), cesium carbonate (578 mg, 1.777 mmol), and DMF (3 ml_). The reaction was degassed (x3) under argon. The reaction was heated at 9O0C for 24 h then allowed to cool to RT, filtered, and the filtrate concentrated in vacuo to afford the title compound (422 mg, quantitative). LCMS (Method 2): Rt 2.20 min, m/z 477 [MH+].

Reference： [1]Patent: WO2010/94956,2010,A1 .Location in patent: Page/Page column 37

42
[ 33252-28-7 ]
[ 4869-59-4 ]
[ 888968-33-0 ]

Yield	Reaction Conditions	Operation in experiment
68%		Add sodium hydride (60% dispersion in mineral oil, 635 mg, 15.88 mmol) to a solution of 3-mercapto-benzoic acid (1.11 g, 7.22 mmol) in dimethylformamide (50 mL) chilled to 00C and stir. After 10 minutes add 6-chloro-nicotinonitrile (1.00 g, 7.22 mmol). Warm gradually to ambient temperature. After 18 hours, add IN aqueous hydrochloric acid (200 mL). Filter resulting precipitate, washing with water and hexanes to yield the title compound as a tan solid (1.25 g, 68%): 1H NMR (DMSO-J6) delta 7.22 (d, IH), 7.67 (t, IH), 7.88 (dt, IH), 8.07-8.12 (m, 3H), 8.82 (dd, IH), 13.30 (bs, IH).

Reference： [1]Patent: WO2006/57860,2006,A1 .Location in patent: Page/Page column 73

43
1-[4-(6-bromo-pyridin-2-ylmethoxy)-2-hydroxy-3-propyl-phenyl]-ethanone [ No CAS ]
[ 4869-59-4 ]
3-[6-(4-acetyl-3-hydroxy-2-propyl-phenoxymethyl)-pyridin-2-ylsulfanyl]-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (361 mg, 2.35 mmol) in dimethylformamide (15 niL) add sodium hydride (23 mg, 9.38 mmol) at 0 C, stir 10 min. Add l-[4-(6-bromo-pyridin-2-ylmethoxy)-2-hydroxy-3-propyl-phenyl]-ethanone (854 mg, 2.35 mmol), heat to 100C for 6 hours. Cool to ambient temperature and add diethyl ether, collect the resulting red precipitate by filtration (290 mg). Purify by the residue by preparative LC (inject 110 mg) to yield the title compound as a white solid (50 mg, 0.12 mmol): 1H NMR (DMSO-J6) delta 0.88 (t, 3H), 1.50 (q, 2H), 2.55 (s, 3 H), 2.61 (m, 2H), 5.25 (s, 2H), 6.65 (d, IH), 6.97 (d, IH), 7.26 (d, IH), 7.62 (t, IH), 7.76 (m, IH), 7.83 (m, IH), 8.02 (m, IH), 8.07 (m, IH), 12.85 (s, IH), 13.25 (br s, IH); MS (m/z): 436 (M-I).

Reference： [1]Patent: WO2006/57860,2006,A1 .Location in patent: Page/Page column 118

44
1-[4-(6-chloro-pyridin-3-ylmethoxy)-2-hydroxy-3-propyl-phenyl]-ethanone [ No CAS ]
[ 4869-59-4 ]
3-[5-(4-acetyl-3-hydroxy-2-propyl-phenoxymethyl)-pyridin-2-ylsulfanyl]-benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Dissolve 3-mercapto-benzoic acid (482 mg, 3.13 mmol, commercially available) in dimethylformamide (20 mL) at 0 0C. Add washed sodium hydride (300 mg), and stir the mixture for 10 minutes. Add l-[4-(6-chloro-pyridin-3-ylmethoxy)-2-hydroxy-3- propyl-phenyl] -ethanone (1.00 g, 3.13 mmol). Stir the mixture at room temperature for 2 hours; then stir at 65 0C for 2 hours and finally stir at 120 0C overnight. Dilute in ethyl acetate, and wash with water twice. Extract the organic layer with saturated aqueous sodium bicarbonate. Acidify the aqueous layer with 2N hydrochloric acidhydrochloric acid to pH 3. Extract with ethyl acetate, wash with brine, dry and concentrate to afford 620 mg of a crude red solid. Purify the residue via chromatography, eluting with 1 : 1 hexane:ethyl acetate to afford the title compound as a light yellow powder (120 mg): 1H NMR (DMSOd6) delta 0.84 (s, 3H), 1.44 (sextet, 2H), 2.55 (t, 2H), 2.58 (s, 3H)5 5.24 (s, 2H), 6.74 (d, IH), 7.14 (d, IH), 7.63 (t, IH), 7.75 (d, IH), 7.81-7.84 (m, 2H), 8.02 (d, IH), 8.05 (s, IH), 8.51 (s, IH), 12.84 (s, IH), 13.21 (bs, IH); MS (APCI-neg mode) mlz (rel intensity) 436 (100).

Reference： [1]Patent: WO2006/57860,2006,A1 .Location in patent: Page/Page column 121-122

45
[ 33252-30-1 ]
[ 4869-59-4 ]
[ 888968-32-9 ]

Yield	Reaction Conditions	Operation in experiment
50%		Add sodium hydride (60% dispersion in mineral oil, 635 mg, 15.88 mmol) to a solution of 3-mercapto-benzoic acid (1.11 g, 7.22 mmol) in dimethylformamide (50 mL) chilled to 00C and stir. After 10 minutes add 2-chloro-isonicotinonitrile (1.00 g, 7.22 mmol). Warm gradually to ambient temperature. After 18 hours, add IN aqueous hydrochloric acid (200 mL). Filter the resulting precipitate, washing with water and hexanes to yield the title compound as a tan solid (920 mg, 50%): 1H NMR (DMSO-J6) delta 7.62-7.66 (m, 3H), 7.84 (d, IH), 8.03-8.08 (m, 2H), 8.62 (d, IH), 13.26 (bs, IH).

Reference： [1]Patent: WO2006/57860,2006,A1 .Location in patent: Page/Page column 73

46
[ 923291-81-0 ]
[ 4869-59-4 ]
[ 923291-83-2 ]

Yield	Reaction Conditions	Operation in experiment
23%		2. 3-[5-(4-Fluorophenylcarbamoyl)pyrimidin-2-ylsulfanyl]benzoic acid To a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (83 mg, 0.54 mmol) in THF (2.5 mL) was added potassium tert-butoxide (1 M in THF, 1.1 ML, 1.1 mmol). After 3 min, 2-methane-sulfinylpyrimidine-5-carboxylic acid (4-fluorophenyl)amide was added in one portion and the solution was stirred for 24 h. Water was added, and then the solution was poured into 3% HCl to precipitate the product. The solids were collected by filtration and washed with water. Flash chromatography on SiO2 using a gradient of 5% methanol/dichloromethane to 10% methanol/dichloromethane afforded 15.1 mg (23% yield) of the titled thioether as a white solid. API-MS m/z 370 (MH+), 368 (M-H)-.

Reference： [1]Patent: US7176310,2007,B1 .Location in patent: Page/Page column 32

47
[ 879402-31-0 ]
[ 4869-59-4 ]
[ 74-88-4 ]
(2S)-N-([4-(3,4-dichlorobenzyl)morpholin-2-yl]methyl)-2-(3-methoxycarbonylphenylthio)acetamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		(41-1) Synthesis of (2S)-N-[4-(3,4-dichlorobenzyl)morpholin-2-yl]methyl}-(3-methoxycarbonylphenylthio)acetamide; <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (840 mg) and the resultant product (2.1 g) of (1-2) were dissolved in dimethylformamide (50 mL), potassium carbonate (2.1 g) was added, and the mixture was stirred at room temperature for 4 hrs. Methyl iodide (0.34 mL) was added, and the mixture was further stirred for 1 hr. Water was poured into the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solvent of chloroform and methanol as an eluent. The solvent was evaporated from the eluent to give the title compound (2.0 g) as a white amorphous solid.

Reference： [1]Patent: EP1801108,2007,A1 .Location in patent: Page/Page column 44

48
[ 5029-67-4 ]
[ 4869-59-4 ]
[ 1192233-60-5 ]

Yield	Reaction Conditions	Operation in experiment
66%	With N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene;tris-(dibenzylideneacetone)dipalladium(0); In 1,4-dioxane; at 100℃;Inert atmosphere;	(Step 1) Production of 3-(pyridin-2-ylthio)benzoic acid Xantphos (3.75 g) and Pd2(dba)3 (2.97 g) were added in that order to a dioxane (150 mL) solution of 2-iodopyridine (7.31 g), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (5.0 g) and N,N-diisopropylethylamine (11.30 mL), and stirred overnight in a nitrogen atmosphere at 100 C. After left cooled, the reaction solution was evaporated under reduced pressure, then ethyl acetate was added to the residue, washed three times with aqueous saturated ammonium chloride solution, and dried with sodium sulfate. The drying agent was removed through filtration, and the solvent was evaporated off under reduced pressure. The residue was purified through silica gel column chromatography (methanol/chloroform=from 0% to 20%, gradient) to give the intended product (4.95 g, 66%) as a brown solid.

Reference： [1]Patent: US2011/9622,2011,A1 .Location in patent: Page/Page column 38

49
[ 1354652-82-6 ]
[ 4869-59-4 ]
[ 1354652-56-4 ]

Yield	Reaction Conditions	Operation in experiment
17%	With triethylamine; In N,N-dimethyl-formamide; at 20℃; for 3h;	Example 3 : 3-(3-((2-((2-phenylpyrimidin-5-yl)carbamoyl -4-(piperidin- 1 -yPphenvQ- carbamoyl benzylthio)benzoic acid.; To a solution of 2-(3-(bromomethyl)benzamido)- N-(2-phenylpyrimidin-5-yl)-5-(piperidin-l-yl)benzamide (120 mg, 0.23 mmol, 1.00 equiv) in N,N-dimethylformamide (10 mL) was added <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (42.12 mg, 0.27 mmol, 1.20 equiv) and triethylamine (46.08 mg, 0.46 mmol, 2.00 equiv) and the resulting solution was stirred for 3 h at room temperature. The mixture was diluted with 70 mL of water, extracted with 3x50 mL of ethyl acetate and the organic layers combined, dried over sodium sulfate, and concentrated under vacuum. The crude product (100 mg) was purified by reverse phase HPLC eluting with a water/CH3CN gradient containing 0.05% TFA to afford 24.7 mg (17%) of a light yellow solid. - NMR (300MHz, DMSO, ppm): delta 10.94(m, 2H), 9.23(d, J=9.3Hz, 2H), 8.36(m, 2H), 8.12(d, J=9Hz, 1H), 7.95(s, 1H), 7.85(s, 1H), 7.73(m, 2H), 7.45 (m, 9H) 4.39(s, 2H), 3.33(s, 4H), 1.72(s, 6H). MS (ES, m/z): 644 [M+H]+.

Reference： [1]Patent: WO2012/6474,2012,A2 .Location in patent: Page/Page column 55

50
[ 1354722-31-8 ]
[ 4869-59-4 ]
[ 1354721-79-1 ]

Yield	Reaction Conditions	Operation in experiment
63%	With N-ethyl-N,N-diisopropylamine; potassium iodide; In tetrahydrofuran; at 40℃; for 24h;	EXAMPLE 183 -((3 -(( 4-(Piperidin- 1 - yl -2-( ( 1 -(3 -(trifluoromethvnphenyl V 1 H-pyrazol-3 - yl carbamoyl phenyl carbamoyl)benzyl)thio benzoic acidInto a 250-mL round bottom flask, was placed a solution of 2-(3- (chloromethyl)benzamido)-5 -(piperidin- 1 -yl)-N-( 1 -(3 -(trifluoromethyl)phenyl)- 1 H- pyrazol-3-yl)benzamide 21a (1.6 g, 2.56 mmol, 1.00 equiv) in tetrahydrofuran (100 mL), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (390 mg, 2.53 mmol, 0.99 equiv), potassium iodide (21.2 mg, 0.13 mmol, 0.05 equiv), and N,N-diisopropylethylamine (660 mg, 5.12 mmol, 2.00 equiv). The resulting solution was stirred for 24 h at 40C in an oil bath. The reaction progress was monitored by TLC/LCMS. The resulting mixture was concentrated under vacuum. The resulting solution was diluted with 20 mL of H20, extracted with 3x20 mL of ethyl acetate and the organic layers combined. The resulting mixture was washed with 1x20 mL of hydrochloric acid (1 mol/L) and 3x20 mL of brine. The mixture was dried over anhydrous sodium sulfate. The residue was applied onto a silica gel column and eluted with ethyl acetate/petroleum ether (1 :20-1 :1). This resulted in 1.12 g (63%) of product as a yellow to green solid. 1H-NMR (400MHz, CDC , ppm): delta 11.68(s, 1H), 9.75(s, 1H), 8.60-8.56(d, J=9.2Hz, 1H), 8.00(s, 1H), 7.91(s, 3H), 7.88-7.81(m, 2H), 7.80-7.79(d, J=2.1Hz, 1H), 7.66-7.65(d, J=2.4Hz, 4H), 7.53-7.38(m, 2H), 7.33-7.25(m, 1H), 7.10-7.08(m, 1H), 4.20(s, 2H), 3.17(s, 4H), 1.69-1.54(m ,6H). MS (ES, m/z): 700 [M+H]+.

Reference： [1]Patent: WO2012/6473,2012,A1 .Location in patent: Page/Page column 96

51
[ 4869-59-4 ]
[ 100-51-6 ]
[ 60739-40-4 ]

Reference： [1]Organic and Biomolecular Chemistry,2012,vol. 10,p. 2942 - 2945
[2]Organic and Biomolecular Chemistry,2014,vol. 12,p. 5964 - 5972

52
[ 1354826-32-6 ]
[ 4869-59-4 ]
[ 1354826-33-7 ]

Yield	Reaction Conditions	Operation in experiment
	With triethylamine; In acetonitrile; at 45℃;	Intermediate 3b: 3-(3-(2-(l-(Phenylsulfonyl -6-(trifluoromethylVlH-indole-2- carbonyl)-4-(piperidin- 1 -yl)phenylcarbamoyl)benzylthio)benzoic acid. Into a 100-mL round-bottom flask was placed a solution of 3-(bromomethyl)-N-(2-(l- (phenylsulfonyl)-6-(trifluoromethyl)- 1 H-indole-2-carbonyl)-4-(piperidin- 1 - yl)phenyl)benzamide (200 mg, 0.28 mmol, 1.00 equiv) in acetonitrile (20 mL), 3- mercaptobenzoic acid (50 mg, 0.32 mmol, 1.20 equiv), and triethylamine (90 mg, 0.89 mmol, 3.00 equiv). The resulting solution was stirred overnight at 45C. The resulting mixture was concentrated under vacuum. The residue was dissolved in 60 ml of ethyl acetate. The resulting mixture was washed with 2x30 mL of water. The mixture was dried over sodium sulfate and concentrated under vacuum. This resulted in 200 mg of intermediate 3b as a red solid.

Reference： [1]Patent: WO2012/6477,2012,A1 .Location in patent: Page/Page column 57

53
[ 1313802-49-1 ]
[ 4869-59-4 ]
[ 1313802-50-4 ]

Yield	Reaction Conditions	Operation in experiment
98%		A 1.03 M solution of 3-benzoate thiolate was prepared from <strong>[4869-59-4]3-mercaptobenzoic acid</strong> and 2.06 M aqueous sodium hydroxide at 100 C for 5 minutes. The solution of 3-benzoate thiolate (0.040 mL, 0.0412 mmol) was added to a solution of l-[3-(bromomethyl)phenyl]-4-phenyl-lH-indole (1) (14.1 mg, 0.0389 mmol) in tetrahydrofuran (0.5 mL), and the mixture was stirred at room temperature for 1 hour. Upon completion, the reaction was diluted with 1.0 M aqueous hydrochloric acid (1 mL), extracted with ethyl acetate (2 mL), the organic layer was washed with brine (10 mL), concentrated, and purified by chromatography (4 g silica gel, 0% to 5% methanol-dichloromethane with 0.5% acetic acid) to afford 3-[3-(4-phenyl- lH-indol-l-yl)benzyl]thio} benzoic acid (2) (16.6 mg, 98% yield) as a clear film; R/0.64 (10% methanol-dichloromethane); 1H NMR (400 MHz, CDC13) delta 8.09 (s, 1H), 7.94 (d, J = 7.7 Hz, 1H), 7.69 (d, J= 7.7 Hz, 2H), 7.55 (d, J= 7.9 Hz, 1H), 7.50-7.21 (m, 12H), 6.82 (d, J= 3.1 Hz, 1H), 4.24 (s, 2H) ppm; LRMS (ESI) m/z [M-H]~ = 434.20.
98%		A 1.03M solution of 3-benzoate thiolate was prepared from <strong>[4869-59-4]3-mercaptobenzoic acid</strong> and 2.06M aqueous sodium hydroxide as above. The solution of 3-benzoate thiolate (0.040mL, 0.0412mmol) was added to a solution of intermediate 1-(3-(bromomethyl)phenyl)-4-phenyl-1H-indole (14.1mg, 0.0389mmol) in tetrahydrofuran (0.5mL), and the mixture was stirred at room temperature for 16h. Upon completion, the reaction was diluted with 1.0 M aqueous hydrochloric acid (1 mL), extracted with ethyl acetate (2 mL), the organic layer was washed with brine (10 mL), concentrated, and purified by chromatography (4 g silica gel, 0-5% methanol-dichloromethane) to afford compound 13, (16.6 mg, 98% yield) as a clear film; 1H NMR (400 MHz, DMSO-d6): delta 7.89 (s, 1H), 7.79 (d, J = 7.68 Hz, 1H), 7.69-7.62 (m, 4H), 7.58-7.50 (m, 4H), 7.48-7.38 (m, 4H), 7.31 (d, J = 7.87 Hz, 1H), 7.24 (t, J = 8.05 Hz, 1H), 7.20 (d, J = 6.59 Hz, 1H), 6.76 (d, J = 3.29 Hz, 1H), 4.43 (s, 2H). Calcd mass for C28H21NO2S: 435.13; LRMS (ESI) m/z [M-H]- = 434.20.

Reference： [1]Patent: WO2011/82098,2011,A1 .Location in patent: Page/Page column 27
[2]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 2253 - 2260

54
[ 4869-59-4 ]
[ 1610566-29-4 ]
[ 1595282-75-9 ]

Yield	Reaction Conditions	Operation in experiment
		General procedure: A 1.0 M solution of L-homocysteine thiolate was prepared by dissolving L-homocysteine thiolactone hydrochloride into 3.0 M aqueous sodium hydroxide at 100 oC for 5 minutes. To a preformed solution of alkyl bromide in ethanol, tetrahydrofuran or N, N-dimethylformamide or mixture with water as indicated, was added aqueous L-homocysteine thiolate solution (1.10 equivalence) and the reaction mixture was stirred at indicated temperature until the completion of reaction as judged by TLC. Upon completion, the reaction mixture was diluted with water (2 mL), extracted with ethyl acetate (2 x 5 mL), the organic layers were discarded and the aqueous layer was acidified with trifluoroacetic acid (200 muL), and concentrated. The residue was dissolved in minimal water (water-methanol mixture were used if the compound did not fully dissolve in water alone), filtered (PALL Life Science, Acrodisc Premium, 25 mm syringe filter with 0.45 micron GHP membrane, catlog AP-4560T) and purified by reverse phase HPLC (XTerra MS, C18 7 micron, 19 x 150 mm column; flow rate 8 mL/minute; UV detection: 254 nm; solvent A: water with 0.1 % trifluoroacetic acid, solvent B: acetonitrile).

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 2253 - 2260

55
[ 4869-59-4 ]
[ 1595282-63-5 ]
[ 1595282-74-8 ]

Yield	Reaction Conditions	Operation in experiment
1.7 mg		A 1.5M solution of 3-benzoate thiolate was prepared by dissolving <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (31.3mg, 0.203mmol) into 2.96M aqueous sodium hydroxide (0.135mL, 0.40mmol) at 100C for 5min. A 0.18M solution of intermediate 5-bromo-1-(3-(bromomethyl)phenyl)-1H-indole (37.3mg, 0.102mmol) in tetrahydrofuran (0.57mL) was added to the aqueous solution, and stirred at room temperature for 16h. Upon completion, the reaction was poured into 1.0M aqueous hydrochloric acid (20mL), extracted with 1:1 ethyl acetate-petroleum ether (30mL), the organic layer was washed with brine (10mL), concentrated, and purified by chromatography (4g silica gel, 0-10% methanol-dichloromethane). A portion of this material was filtered (PALL Life Sciences, Acrodisc Premium, 25mm syringe filters with 0.45 micron GHP membrane, catalog AP-4560T), purified by reverse phase HPLC (VYDAC Cl8 , 11×250mm column; flow rate 6mL/min; UV detection: 254nm; solvent A: water with 0.1% ammonium hydroxide, solvent B: acetonitrile; gradient run: 5% B for 3min then ramp to 40% B over 25min), and neutralized to afford compound 11, (1.7mg) as a clear film; 1H NMR (400MHz, CDCl3): delta 7.88 (s, 1H), 7.86 (d, J=12.99Hz, 1H), 7.77 (d, J=7.68Hz, 1H), 7.60-7.65 (m, 2H), 7.49-7.54 (m, 2H), 7.40-7.47 (m, 3H), 6.68 (d, J=3.29Hz, 1H), 4.41 (s, 2H). Calcd mass for C22H16BrNO2S: 437.01; LRMS (ESI) m/z [M-H]-=436.21/438.28 (bromine pattern).

Reference： [1]Bioorganic and Medicinal Chemistry,2014,vol. 22,p. 2253 - 2260

56
[ 4869-59-4 ]
[ 622-95-7 ]
[ 1367928-40-2 ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium hydroxide; In ethanol; water; for 24h;Reflux;	General procedure: A mixture of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (1 g, 7.25 mmol), KOH (0.89 g, 0.016 mmol), and benzyl bromide (7.97 mmol) in ethanohwater (16 mL/2 mL) was heated under reflux for 20 h. Aqueous KOH solution (20%, 10 mL) was added, and the mixture was heated under reflux for a further 4 h. The reaction mixture was allowed to cool, water was added, and the solution was acidified with 2 N HC1. The precipitate was filtered off and dried in vacuo to give the desired products (165-167), which were carried forward without further purification. [0235] 3-((4-chlorobenzyl)thio)benzoic acid (165). Compound 165 was prepared according to procedure G to afford 1819 mg of white powder (90%). 1H NMR (500 MHz, CDCls) delta 4.14 (s, 2H), 7.22 - 7.27 (m, 4H), 7.36 (t, J = 7.8Hz, 1H), 7.47 (dt, J = 1.6, 7.9Hz, 1H), 7.92 (dd, J = 1.1, 7.8Hz, 1H), 8.05 (t, J = 1.6Hz, 1H). 13C NMR (126 MHz, CDCI3) delta 41.96, 131.69, 132.48, 132.66, 134.05, 134.73, 136.23, 136.88, 137.66, 139.59, 140.06, 173.24.

Reference： [1]Patent: WO2014/100833,2014,A1 .Location in patent: Paragraph 0082; 0235
[2]ACS Medicinal Chemistry Letters,2015,vol. 6,p. 607 - 611

57
[ 4869-59-4 ]
Fe(α-benzyldioxime)₂(chloroglyoxime(morpholine))(BF)₂ [ No CAS ]
Fe(α-benzyldioxime)₂((meta-mercaptobenzoicacid)glyoxime(morpholine))(BF)₂ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
63%	With triethylamine; In dichloromethane;	3.3 FeBd2((meta-HOOCC6H4S)Gm(morph))(BF)2 This complex was obtained by the similar procedure, except then <strong>[4869-59-4]meta-mercaptobenzoic acid</strong> (0.074 g, 0.48 mmol) was used instead of para-mercaptobenzoic acid. Yield: 0.11 g (63%). Anal. Calc. for C41H33N7B2F2FeO9S: C, 53.77; N, 10.71; H, 3.61; Fe, 6.12. Found: C, 53.59; N, 10.57; H, 3.57; Fe, 5.95%. MS (MALDI-TOF) m/z (I,%): 916 (100) [M]+?, 939 (30) [M+Na+]+, 955 (30) [M+K+]+. 1H NMR (CD2Cl2) delta (ppm) 3.19 (m, 4H, CH2N), 3.52 (m, 4H, CH2O), 7.27 (m, 21H, Ph), 7.55 (m, 1H, Ph), 7.80 (m, 1H, Ph) 7.87 (m, 1H, Ph). 13?{1H} NMR (CD2Cl2) delta (ppm) 51.4 (s, CH2N), 68.8 (s, CH2O), 130.0, 131.1, 131.8, 132.1, 132.5, 132.9, 135.0, 136.8 (all s, Ph), 147.2 (s, NC=N), 154.0 (s, SC=N), 159.0, 160.1 (both s, PhC=N), 171.8 (s, COOH). IR (KBr) nu/cm-1: 930, 1001, 1060, 1107, 1174 nu(N-O), 1212m nu(B-O) + nu(B-F), 1589m nu(C=N), 1716 nu(C=O). UV-Vis (CH2Cl2): lambdamax/nm (epsilon·10-3 mol-1·L·cm-1) 258 (27), 289 (15), 307 (6.2), 355 (4.3), 453 (5.2), 484 (17), 520 (8.6).

Reference： [1]Inorganica Chimica Acta,2014,vol. 421,p. 300 - 306

58
[ 91-01-0 ]
[ 4869-59-4 ]
[ 1619971-25-3 ]

Reference： [1]Organic and Biomolecular Chemistry,2014,vol. 12,p. 5964 - 5972
[2]Advanced Synthesis and Catalysis,2016,vol. 358,p. 395 - 402
[3]Organic and Biomolecular Chemistry,2016,vol. 14,p. 7038 - 7045

59
[ 4869-59-4 ]
[ 10199-89-0 ]
3-((7-nitrobenzo[c][1,2,5]oxadiazol-4-yl)thio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
64%	With pyridine; In ethanol; water; at 20℃; for 7h;	General procedure: Pyridine (0.69 mL, 8.62 mmol) and 4-mercaptobenzoic acid (462.6 mg, 3.0 mmol) were added to a solution of 4-chloro-7-nitrobenzo[c][1,2,5]oxadiazole (688.4 mg, 3.45 mmol) in a mixture (18 mL) EtOH:H2O (0.3:1). The mixture was stirred at room temperature for 7 h. Afterward, the suspension was filtered and the crude solid was washed on the filter with H2O. The compound obtained was first purified by trituration with CHCl3 and then by column chromatography on SiO2 gel eluting with a mixture CHCl3/MeOH (10:1).

Reference： [1]European Journal of Medicinal Chemistry,2015,vol. 89,p. 156 - 171

60
[ 4869-59-4 ]
[ 540-51-2 ]
3-[(2-hydroxyethyl)sulfanyl]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
94%	With sodium hydride; In ethanol; at 20℃; for 2h;	Step 1: 3-[(2-Hydroxyethyl)sulfanyl]benzoic acid Sodium hydride (0.45 g, 19 mmol) was added slowly to a solution of m-mercaptobenzoicacid (0.97 g, 6.3 mmol) in ethanol (25.0 mL) a rt. Then, 2-bromoethanol (0.79 g, 6.3 mmol) was added to this solution at rt and the resulting mixture was allowed to stir for 2 h at rt. Acetic acid (5 mL) was added to the solution and the mixture was concentrated. Water (30 mL) was added to dissolve the crude residue and the mixture was extracted with DCM (2x). The combined organic layers were dried over MgS04, filtered and concentrated to provide 3-[(2-hydroxyethyl)sulfanyl]benzoic acid (1.2 g, 94%).

Reference： [1]Patent: WO2015/2994,2015,A2 .Location in patent: Paragraph 00239

61
[ 4073-59-0 ]
[ 4869-59-4 ]
C₁₂H₁₅O₄PS₃ [ No CAS ]

Reference： [1]RSC Advances,2015,vol. 5,p. 31347 - 31351

62
[ 4869-59-4 ]
[ 459-57-4 ]
3-((4-formylphenyl)thio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		To a solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (0.5 g, 3.3 mmol, 1.0 eq) in DMF (5 mL) was added EtONa (2.1 g, 21% in EtONa, 6.5 mmol, 2.0 eq) at 0 C under N2. The mixture was stirred at 0 C for 30 min, then 4- fluorobenzaldehyde (0.4 g, 3.3 mmol, 1.0 eq) was added into the mixture. The reaction mixture was stirred at rt overnight. The reaction mixture was poured into ice-water (10 mL), acidified with 1 N HCl to pH 3-4. The mixture was concentrated to dryness under reduced pressure. The residue was re-dissolved in MeOH (20 mL) and filtered. The filtrate was concentrated under reduced pressure. The residue was purified via flash chromatography to afford 3-((4-formylphenyl)thio)benzoic acid as a yellow solid (1.1 g, about 50%> purity, 64%).

Reference： [1]Patent: WO2015/103317,2015,A1 .Location in patent: Page/Page column 118

63
[ 4869-59-4 ]
[ 77369-59-6 ]
3-(4-aminobut-2-ynylsulfanyl)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With N-ethyl-N,N-diisopropylamine; In isopropyl alcohol; at 120℃; for 16h;	Step 1. A mixture of <strong>[4869-59-4]3-sulfanylbenzoic acid</strong> (3 equiv.), 4-chlorobut-2-yn-1-aminehydrochloride (1 equiv.), and Hunig?s base (6 equiv.) in 2-propanol was stirred at120 00 for 16 h. A precipitate formed which was collected by filtration and washed with MeOH and DCM to afford 3-(4-aminobut-2-ynylsulfanyl)benzoic acid. LCMS [M+H] 222.
	With N-ethyl-N,N-diisopropylamine; In isopropyl alcohol; at 120℃; for 16h;	Step 1. A mixture of <strong>[4869-59-4]3-sulfanylbenzoic acid</strong> (3 equiv.), 4-chlorobut-2-yn-1 -amine hydrochloride (1 equiv.), and Hunig's base (6 equiv.) in 2-propanol was stirred at 120 C for 16 h. A precipitate formed which was collected by filtration and washed with MeOH and DCM to afford 3-(4-aminobut-2-ynylsulfanyl)benzoic acid. LCMS [M+H]+ 222.

Reference： [1]Patent: WO2015/187088,2015,A1 .Location in patent: Page/Page column 115
[2]Patent: WO2015/187089,2015,A1 .Location in patent: Page/Page column 290

64
[ 4869-59-4 ]
[ 1129-28-8 ]
3-(3-(methoxycarbonyl)benzylthio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
90%	With potassium carbonate; In N,N-dimethyl-formamide; for 16h;	A mixture of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (154 mg, 1.00 mmol), methyl 3-(bromomethyl)benzoate (229 mg, 1.00 mmol) and K2CO3 (414 mg, 3.00 mmol) in DMF (1 mL) was stirred for 16 h, then solvent removed. The resulting residue was purified by silica gel chromatography to give 300 mg (90%) of the product.

Reference： [1]Patent: US9301951,2016,B2 .Location in patent: Page/Page column 367

65
[ 4869-59-4 ]
[ 25440-14-6 ]
C₇₂H₃₀F₁₆N₄O₈S₄ [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
85%		In a round-bottom flask, 0.24 mmol of <strong>[4869-59-4]3-mercaptobenzoic acid</strong>were dissolved in 20 mL of DMF with 1.0 mL of pyridine and keptunder magnetic stirring at room temperature for 30 min. After thistime the porphyrin P1 (0.035 mmol) was added and the reactionmixture was kept under magnetic stirring for 48 h. The reactionwas monitored by TLC and the reaction was stopped when no P1was detected. The solvent was evaporated under reduced pressure and the crude material dissolved in CH2Cl2:CH3OH was purified bycolumn chromatography using silica as the stationary phase andCH2Cl2:CH3OH (9:1 v/v) as eluent. Porphyrin P3 was obtained in85% yield, after crystallization from a mixture ofCH2Cl2:CH3OH:hexane.Porphyrin P3, mp > 300 C: deltaH ppm (DMSO-d6): -3.13 (s, 2H,NH), 7.72 to 7.67 (t, J = 7.8 Hz, 4H, S-C6H4-CO2H), 8.06 to 7.97 (m,8H, S-C6H4-CO2H), 8.23 (s, 4H, S-C6H4-CO2H) and 9.50 (s, 8H, H-b).19F NMR: dF ppm (DMSO-d6) -161.2 to 161.1 (dd, J = 11.4 and26.6 Hz, 8F, F-meta), and -156.7 to -156.6 (dd, J = 11.4 and 26.6 Hz,8F, F-ortho) (see ESI). UV-VIS (DMF) lmax, nm(log epsilon): 412 (5.14), 504(4.07), 582 (3.57). HRMS-ESI: calcd. for C72H29F16N4O8S4 [M - H]+.1509.0764 found 1509.0657; calcd. for C72H30F16N4O8S4 [M+.]1510.0691 found 1510.0683; calcd. for C72H31F16N4O8S4 [M+H]+1511.0725 found 1511.0687.

Reference： [1]Dyes and Pigments,2017,vol. 137,p. 265 - 276

66
[ 4869-59-4 ]
[ 75-03-6 ]
[ 5537-74-6 ]

Reference： [1]Angewandte Chemie - International Edition,2016,vol. 55,p. 11193 - 11197
Angew. Chem.,2016,vol. 128,p. 11359 - 11363,5

67
[ 33924-45-7 ]
[ 4869-59-4 ]
3-[(2-bromo-4-chlorophenyl)methylsulfanyl]benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
95%	With triethylamine; In acetonitrile; at 45℃; for 20h;	Triethylamine (736 muL, 5.27 mmol, 3.0 eq) is added at room temperature to a stirred solution of 2-bromo-1- (bromomethyl)-4-chloro-benzene (500 mg, 1.76 mmol, 1.0 eq) [33924-45-7] and <strong>[4869-59-4]3-sulfanylbenzoic acid</strong> (298 mg, 1.93 mmol, 1.1 eq) [4869-59-4] in acetonitrile (10 mL). After 20 hours stirring at 45C, the reaction mixture is concentrated to afford 3-[(2-bromo-4-chloro-phenyl)methylsulfanyl]benzoic acid as an off-white solid (600 mg, 95% yield) that is directly engaged in the next step without further purification. 1H-NMR (400 MHz, CDCl3) ^ ppm: 8.10 (d, J = 1.6 Hz, 1H), 7.98 (d, J = 7.6 Hz, 1H), 7.60 (d, J = 0.9 Hz, 1H), 7.53 (d, J = 7.6 Hz, 1H), 7.40 (m, 1H), 7.20 (m, 2H), 4.24 (s, 2H). MS m/z (+ESI): 355.0, 357.0 [M+H]+

Reference： [1]Patent: WO2016/198691,2016,A1 .Location in patent: Page/Page column 172

68
[ 2160-62-5 ]
[ 4869-59-4 ]
[ 74-88-4 ]
methyl 3-((5-(cyano)thiophen-2-yl)thio)benzoate [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
78%		[00751] A mixture of <strong>[2160-62-5]5-bromothiophene-2-carbonitrile</strong> (406 mg, 2.83 mmol), 3-mercaptobenzoic acid (479 mg, 3.1 1 mmol), and K2CO3 (781 mg, 5.65 mmol) in DMF (1 1 mL) was stirred at 120C for 16 h. After cooling to rt, Mel (406 muIota_, 6.52 mmol) and K2CO3 (273 mg, 1 .98 mmol) were added and the mixture was stirred at 50 C for 1 h. More Mel (406 muIota_) was added and the mixture was stirred at 50 C for a further 1 .5 h. EtOAc was added and the organic phase was washed with H20/brine 1 :1 (3 x), dried over Na2S04 and filtered. The solvent was removed under reduced pressure and the crude was purified on by chromatography (DCM) to afford methyl 3-((5-(cyanomethyl)thiophen-2-yl)thio)benzoate as a brown oil (61 1 mg, 78%). To a solution of methyl 3-((5-(cyanomethyl)thiophen-2-yl)thio)benzoate (61 1 mg, 2.22 mmol) in THF (20 mL) was added BF3.THF complex (1 .0 M in THF; 6.6 mL, 6.60 mmol). The mixture was stirred for at rt for 1 h, and then quenched with EtOH. The mixture was heated at reflux for 1 h before the solvent was removed under reduced pressure. DCM (40 mL) was added, followed by Et3N (620 mu, 4.45 mmol) and FJ0C2O (1 .45 g, 6.65 mmol). The mixture was stirred at rt for 16 h and then diluted with DCM. The organic phase was washed with H2O, dried over Na2S04, filtered and the solvent was removed under reduced pressure. The crude was purified by chromatography (EtOAc/cyclohexane 0?30%) to afford methyl 3-((5-(((fe/f- butoxycarbonyl)amino)methyl)thiophen-2-yl)thio)benzoate as a sticky yellow oil (482 mg, 57%). H NMR (500 MHz, MeOD) delta 7.75 (d, J = 7.3 Hz, 1 H), 7.80 (m, 1 H), 7.30 (m, 2H), 7.15 (d, J = 3.6 Hz, 1 H), 6.94 (d, J = 3.7 Hz, 1 H), 4.81 (s, 1 H), 4.39 (s, 2H), 3.84 (s, 3H), 1 .43 (s, 9H).

Reference： [1]Patent: WO2017/141049,2017,A1 .Location in patent: Paragraph 00751

69
[ 4869-59-4 ]
methyl(([1,2,4]triazolo-[4,3-a]pyridin-3-yl)methyl)amine hydrochloride [ No CAS ]
3-mercapto-N-methyl-N-(([1,2,4]triazolo[4,3-a]pyridin-3-yl)methyl)benzamide [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
30%	With N-ethyl-N,N-diisopropylamine; N-[(dimethylamino)-3-oxo-1H-1,2,3-triazolo[4,5-b]pyridin-1-yl-methylene]-N-methylmethanaminium hexafluorophosphate; In N,N-dimethyl-formamide; at 20℃; for 2h;	General procedure: General synthetic procedure for synthesis of amide derivatives of methyl-[1,2,4]triazolo[4,3-a]pyridin-3-ylmethylamine (8a-8k): To a stirred solution of compound 7 (100 mg, 1.0 equiv) in DMF (3 mL) was added 4-bromo-2-methyl-benzoic acid (241.32 mg, 1.1 equiv). To this mixture DIPEA (0.526 mL, 3.0 equiv) followed by HATU (387.84 mg,1.0 equiv) were added at ambient temperature. The reaction mixture was stirred at the same temperature for 2 h. Reaction was monitored by TLC (8:2 EtOAc and methanol), which showed complete consumption of the starting material. The reaction mixture was basified with sat. NaHCO3. The aqueouslayer was extracted with dichloromethane (3 × 100 mL). The combined organic layers were washed with brine, dried over Na2SO4 and evaporated under reduced pressure to afford crude product. The crude was purified by silica-gel (100-200) column chromatography using 5 % methanol/ethylacetate as an elluent to afford 4-bromo-2,N-dimethyl-N-[1,2,4]triazolo[4,3-a]-pyridin-3-ylmethyl benzamide (8a) (30 mg, 70 %) as a offwhitesolid. Same procedure was adopted for the synthesis of remaining compounds 8b-8k.

Reference： [1]Asian Journal of Chemistry,2017,vol. 29,p. 1920 - 1924

70
[ 4869-59-4 ]
C₆H₁₂Cl₂N₂O₂Sn [ No CAS ]
C₁₀H₁₂Cl₂N₂O₂SSn [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
40%	In ethanol; for 0.5h;Reflux;	Solutions of (H2NCOCH2CH2-C,O)2SnCl2 (0.30 g, 1 mmol) inethanol (10 ml) and 2-HSC6H4CO2H (0.16 g, 1 mmol) in ethanolwere mixed and refluxed for 30 min. The reaction mixturewas concentrated to 10 ml and left at room temperature.The solid, which slowly formed, was collected after three days,and further recrystallized twice from cold ethanol solution toyield colourless blocks of 3. Final yield, 0.08 g (40%), m.p.175-178C. 1HNMR (DMSO) d: 7.68 (d, 1H), 7.35 (br, d, 1H), 7.08(m, 1H), 6.98 (m, 1H), [all aryl H atoms] 5.85 (br, 1H, NH), 5.62(br, 1H, NH), 2.85 (t, J 7 Hz, 2H, CH2), 2.45 (t, J 7 Hz), 2H,CH2). Anal.: calc. for C10H12Cl2N2O2SSn: C 29.02, H 2.44, N6.76%: found: C 29.24, H 2.41, N 6.92%. IR (cm1) 3300-2700,1645(s).

Reference： [1]Journal of Organometallic Chemistry,2017,vol. 848,p. 318 - 324

71
[ 15963-46-9 ]
[ 4869-59-4 ]
3-((3-(methoxycarbonyl)cyclobutyl)thio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
2.02 g	With potassium carbonate; In N,N-dimethyl-formamide; at 50℃; for 16h;	Step 1: Preparation of 3-((3-(Methoxycarbonyl)cyclobutyl)thio)benzoic Acid, Intermediate 20.0 A mixture of 3-mercaptobenzoic acid (2.1 g, 13.5 mmol), <strong>[15963-46-9]methyl 3-chlorocyclobutanecarboxylate</strong> (4.0 g, 26.9 mmol; purchased as a 9:1 diastereomeric mixture (favoring trans) from Synthonix, Inc.), and potassium carbonate (7.43 g, 53.8 mmol) in DMF was stirred at 50 C. for 16 h. The reaction mixture was diluted with water and extracted with EtOAc. The combined organic layers were washed with brine, dried over MgSO4, and concentrated under reduced pressure. The crude material was purified by MPLC using silica gel and eluting with a 0-40% EtOAc/EtOH (3:1) in heptane to provide 3-((3-(methoxycarbonyl)cyclobutyl)thio)benzoic acid (2.02 g) as white powder. 1H NMR (400 MHz, DMSO-d6) delta 12.91-13.22 (m, 1H), 7.74-7.77 (m, 2H), 7.44-7.49 (m, 2H), 3.96 (tt, J=7.77, 8.97 Hz, 1H), 3.56-3.61 (m, 3H), 3.11-3.23 (m, 1H), 2.67-2.73 (m, 2H), 2.10-2.21 (m, 2H). LCMS-ESI (POS.) m/z: 289.0 (M+Na)+.

Reference： [1]Patent: US2019/77793,2019,A1 .Location in patent: Paragraph 0259

72
[ 4869-59-4 ]
[ 96-34-4 ]
[ 299181-78-5 ]

Yield	Reaction Conditions	Operation in experiment
	With potassium carbonate; In acetonitrile; at 20℃; for 2h;	Step 1: Preparation of 3-((2-methoxy-2-oxoethyl)thio)benzoic Acid A 50 mL round-bottom flask with was charged with anhydrous potassium carbonate (610 mg, 4.41 mmol), <strong>[4869-59-4]3-mercaptobenzoic acid</strong> (340 mg, 2.205 mmol, TCl America), chloroacetic acid methyl ester (193 muL, 2.21 mmol) and acetonitrile (4.4 mL). The reaction was stirred at rt for 2 h then diluted with water (10 mL). The pH was adjusted to 1 using 6N HCl and then extracted with DCM (3*25 mL). The combined organics were washed with brine, passed through phase separation filter, and concentrated to give a white solid that was used without further purification. LCMS-ESI (POS.) m/z: 249.0 (M+Na)+.

Reference： [1]Patent: US2019/77793,2019,A1 .Location in patent: Paragraph 0254

73
[ 1231691-29-4 ]
[ 4869-59-4 ]
6-(3-carboxyphenylthio)-3-(3,5-dimethyl-1H-pyrazol-1-yl)imidazo[1,2-b][1,2,4,5]tetrazine [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
20%	With triethylamine; In acetonitrile; at 20℃; for 48h;	General procedure: To a solution of 31 imidazo[1,2-b][1,2,4,5]tetrazine 1a-d, 2 (1mmol) in 32 acetonitrile (5mL), thiol (1.1mmol) and 33 triethylamine (101mg, 1mmol) were added. The reaction mixture was stirred 1h for compounds 3f-i,l, 3h - 3o,p 5-7h - 3a-c, 24h - 3d,e,j,n, 48h - 3k,m,5at room temperature (TLC control). The solvent was concentrated. Compounds 3a-i,n-p, 5 were isolated by column chromatography (Rf=0.43-0.92), 34 3m were isolated by preparative HPLC (Rf=0.68), 3j,k were isolated by recrystallization from methanol, 3l - from ethanol.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 178,p. 39 - 47

74
[ 4869-59-4 ]
[ 71939-50-9 ]
10β-S-[3'-(carboxyphenyl)]-10-deoxoartemisinin [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
76%	With boron trifluoride diethyl etherate; In dichloromethane; at -20℃;	To a solution of dihydroartemisinin (2, 500mg, 1.76mmol) in dry CH2Cl2 held at-20C (10mL), the desired thiol-bearing carboxylic/ester moiety (1.2mol equiv) was added. BF3. Et2O (0.22mL, 1mol equiv) was then added to it after 5min; and the stirring was continued until TLC (CH2Cl2/MeOH, 5%) showed completion of the reaction (10-20min). The reaction mixture was extracted with CH2Cl2 and was washed thrice with ice-cold water. The organic layer was then dried over anhydrous sodium sulfate. It was then concentrated under reduced pressure to a small volume and was chromatographed on silica gel (230-400 mesh) column using CH2Cl2/MeOH as the eluent. Characterization of the isolated product by physical methods of analysis confirmed the respective structure.

Reference： [1]European Journal of Medicinal Chemistry,2019,vol. 178,p. 552 - 570

75
[ 27060-75-9 ]
[ 4869-59-4 ]
3-((4-methoxy-2-methylphenyl)thio)benzoic acid [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
	With tris-(dibenzylideneacetone)dipalladium(0); N-ethyl-N,N-diisopropylamine; 4,5-bis(diphenylphos4,5-bis(diphenylphosphino)-9,9-dimethylxanthenephino)-9,9-dimethylxanthene; In 1,4-dioxane; at 90℃; for 16h;Inert atmosphere; Sealed tube;	To a stirred solution of <strong>[4869-59-4]3-mercaptobenzoic acid</strong> 1 (200 mg, 1.3 mmol) in l,4-dioxane (8 mL) were added l-bromo-4-methoxy-2-methylbenzene 2 (0.21 mL, 1.56 mmol), NJV- diisopropylethylamine (0.68 mL, 3.9 mmol) followed by Xantphos (150 mg, 0.26 mmol) in a sealed tube at RT under inert atmosphere and purged under argon for 15 min. To this reaction mixture was added Pd2(dba)3 (238 mg, 0.26 mmol) at RT. The vessel was sealed and heated to 90 C and stirred for 16 h. The progress of the reaction was monitored by TLC; after the completion, the reaction mixture was filtered through a pad of celite and the celite bed was washed with EtOAc (20 mL). The filtrate was concentrated under reduced pressure to obtain the crude. The crude material was purified by silica gel column chromatography (eluent: 2% MeOH/CLLCh) to afford compound 3 (130 mg, impure) as brown syrup. This material was taken to next step without further purification. LC-MS: in z 272.9 [M-H]- at 2.63 RT (29.28% purity).

Reference： [1]Patent: WO2019/213148,2019,A1 .Location in patent: Page/Page column 85

76
[ 107-98-2 ]
[ 1953-99-7 ]
[ 4869-59-4 ]
C₁₉H₁₃Cl₃N₂O₅S [ No CAS ]

Yield	Reaction Conditions	Operation in experiment
		Tetrachlorophthalonitrile (26.6 parts by weight),m-mercaptobenzoic acid (15.4 parts by weight),To a solution of dimethylformamide (200 parts by weight),Add potassium carbonate (15 parts by weight)The reaction was allowed to proceed for 1 hour at room temperature.Subsequently, thionyl chloride (50 parts by weight) was added and reacted at 70 C. for 1 hour. After cooling to room temperature, 1-methoxy-2-propanol (10 parts by weight) was added, and the mixture was further heated to reflux for 4 hours. .After completion of the reaction, liquid separation with ethyl acetate and 1N aqueous hydrochloric acid was performed.The organic layer was concentrated and purified by silica gel column chromatography. Subsequently, sodium tungstate for the purified sample(5 parts by weight), hydrogen peroxide (30%, 6.8 parts by weight) acetic acid(5 parts by weight) and ethanol (50 parts by weight) were added and stirred at 50 C. for 5 hours. After completion of the reaction, separation and purification by silica gel column chromatography gave Intermediate A-103 (10 parts by weight).

Reference： [1]Patent: JP5914052,2016,B2 .Location in patent: Paragraph 0120

77
[ 4869-59-4 ]
[ 75-08-1 ]
3-(ethyldisulfanyl)benzoic acid [ No CAS ]

Reference： [1]ChemMedChem,2020

78
[ 49763-41-9 ]
[ 4869-59-4 ]
[ 354810-55-2 ]

Yield	Reaction Conditions	Operation in experiment
91%	With sodium hydroxide In water; acetonitrile at 50℃;	Preparation of Cy3PAu(2-mba) (1) General procedure: NaOH (0.5 mmol, 0.020 g) in water (5 mL) wasadded to a suspension of Cy3PAuCl (0.5 mmol,0.256 g) in acetonitrile (20 mL), followed by additionof 2-mercaptobenzoic acid (0.5 mmol, 0.077 g) in 20 mL acetonitrile and the resulting mixture wasstirred for 3 h at 50 C. The solution mixture wasextracted with dichloromethane and added withequivolume of acetonitrile, which was left for slowevaporation at room temperature, yielding crystalsafter 2 weeks. Using the same procedures, compounds2 and 3 were prepared and crystallised similarly.

Reference： [1]Ang, Kok Pian; Chan, Pit Foong; Hamid, Roslida Abd [BioMetals, 2021, vol. 34, # 1, p. 141 - 160]

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P308 + P313	IF exposed or concerned: Get medical advice/attention.
P309 + P311	IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician.
P332 + P313	IF SKIN irritation occurs: Get medical advice/attention.
P333 + P313	IF SKIN irritation or rash occurs: Get medical advice/attention.
P335 + P334	Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages.
P337 + P313	IF eye irritation persists: Get medical advice/attention.
P342 + P311	IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician.
P370 + P376	In case of fire: Stop leak if safe to Do so.
P370 + P378	In case of fire:
P370 + P380	In case of fire: Evacuate area.
P370 + P380 + P375	In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion.
P371 + P380 + P375	In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion.
Storage
Code	Phrase
P401
P402	Store in a dry place.
P403	Store in a well-ventilated place.
P404	Store in a closed container.
P405	Store locked up.
P406	Store in corrosive resistant/ container with a resistant inner liner.
P407	Maintain air gap between stacks/pallets.
P410	Protect from sunlight.
P411
P412	Do not expose to temperatures exceeding 50 oC/ 122 oF.
P413
P420	Store away from other materials.
P422
P402 + P404	Store in a dry place. Store in a closed container.
P403 + P233	Store in a well-ventilated place. Keep container tightly closed.
P403 + P235	Store in a well-ventilated place. Keep cool.
P410 + P403	Protect from sunlight. Store in a well-ventilated place.
P410 + P412	Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF.
P411 + P235	Keep cool.
Disposal
Code	Phrase
P501	Dispose of contents/container to ...
P502	Refer to manufacturer/supplier for information on recovery/recycling

Physical hazards
Code	Phrase
H200	Unstable explosive
H201	Explosive; mass explosion hazard
H202	Explosive; severe projection hazard
H203	Explosive; fire, blast or projection hazard
H204	Fire or projection hazard
H205	May mass explode in fire
H220	Extremely flammable gas
H221	Flammable gas
H222	Extremely flammable aerosol
H223	Flammable aerosol
H224	Extremely flammable liquid and vapour
H225	Highly flammable liquid and vapour
H226	Flammable liquid and vapour
H227	Combustible liquid
H228	Flammable solid
H229	Pressurized container: may burst if heated
H230	May react explosively even in the absence of air
H231	May react explosively even in the absence of air at elevated pressure and/or temperature
H240	Heating may cause an explosion
H241	Heating may cause a fire or explosion
H242	Heating may cause a fire
H250	Catches fire spontaneously if exposed to air
H251	Self-heating; may catch fire
H252	Self-heating in large quantities; may catch fire
H260	In contact with water releases flammable gases which may ignite spontaneously
H261	In contact with water releases flammable gas
H270	May cause or intensify fire; oxidizer
H271	May cause fire or explosion; strong oxidizer
H272	May intensify fire; oxidizer
H280	Contains gas under pressure; may explode if heated
H281	Contains refrigerated gas; may cause cryogenic burns or injury
H290	May be corrosive to metals
Health hazards
Code	Phrase
H300	Fatal if swallowed
H301	Toxic if swallowed
H302	Harmful if swallowed
H303	May be harmful if swallowed
H304	May be fatal if swallowed and enters airways
H305	May be harmful if swallowed and enters airways
H310	Fatal in contact with skin
H311	Toxic in contact with skin
H312	Harmful in contact with skin
H313	May be harmful in contact with skin
H314	Causes severe skin burns and eye damage
H315	Causes skin irritation
H316	Causes mild skin irritation
H317	May cause an allergic skin reaction
H318	Causes serious eye damage
H319	Causes serious eye irritation
H320	Causes eye irritation
H330	Fatal if inhaled
H331	Toxic if inhaled
H332	Harmful if inhaled
H333	May be harmful if inhaled
H334	May cause allergy or asthma symptoms or breathing difficulties if inhaled
H335	May cause respiratory irritation
H336	May cause drowsiness or dizziness
H340	May cause genetic defects
H341	Suspected of causing genetic defects
H350	May cause cancer
H351	Suspected of causing cancer
H360	May damage fertility or the unborn child
H361	Suspected of damaging fertility or the unborn child
H361d	Suspected of damaging the unborn child
H362	May cause harm to breast-fed children
H370	Causes damage to organs
H371	May cause damage to organs
H372	Causes damage to organs through prolonged or repeated exposure
H373	May cause damage to organs through prolonged or repeated exposure
Environmental hazards
Code	Phrase
H400	Very toxic to aquatic life
H401	Toxic to aquatic life
H402	Harmful to aquatic life
H410	Very toxic to aquatic life with long-lasting effects
H411	Toxic to aquatic life with long-lasting effects
H412	Harmful to aquatic life with long-lasting effects
H413	May cause long-lasting harmful effects to aquatic life
H420	Harms public health and the environment by destroying ozone in the upper atmosphere

[ CAS No. 4869-59-4 ] {[proInfo.proName]}

Quality Control of [ 4869-59-4 ]

Related Doc. of [ 4869-59-4 ]

Product Details of [ 4869-59-4 ]

Calculated chemistry of [ 4869-59-4 ]

Physicochemical Properties

Pharmacokinetics

Lipophilicity

Druglikeness

Water Solubility

Medicinal Chemistry

Safety of [ 4869-59-4 ]

Application In Synthesis of [ 4869-59-4 ]

[ 4869-59-4 ] Synthesis Path-Upstream 1~3

[ 4869-59-4 ] Synthesis Path-Downstream 1~78

Related Functional Groups of [ 4869-59-4 ]

Aryls

Carboxylic Acids

Related Parent Nucleus of [ 4869-59-4 ]

Thiophenols

Precautionary Statements-General

Prevention

Response

Storage

Disposal

Physical hazards

Health hazards

Environmental hazards

Inquiry

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[ 4869-59-4 ]

Related Parent Nucleus of
[ 4869-59-4 ]